1

Supporting Information for

Formation of Chlorobenzenes by Oxidative Thermal Decomposition

of 13-Dichloropropene httpdxdoiorg101016jcombustflame201502008

Nwakamma Ahubelema Kalpit Shaha Behdad Moghtaderia Mohammednoor Altarawnehab

Bogdan Z Dlugogorskiab Alister J Pagea

a Newcastle Institute for Energy and Resources The University of Newcastle Callaghan NSW

2308 Australia

b School of Engineering and Information Technology Murdoch University Murdoch WA 6150

Australia

2

Activation steps in the thermal decomposition of 13-Dichloropropene

C-Cl bond scission in 13-D (species R1 see Scheme S1) can take place at either the

vinylic or allylic carbons forming two distinct radicals IM1 and IM16 Computed reaction

enthalpies indicate that C-Cl fission from a vynilic site is barrierless and endothermic by

3713 kJmol Scission of the allylic C-Cl bond is the more favourable pathway being

endothermic by 2573 kJmol This follows since sp2-hybridized carbon exhibit more s

character than sp3-hybridized carbon and thus form shorter and stronger bonds An

alternative pathway to IM1IM16 formation is Cl abstraction from 13-D by ambient Cl

radicals (see Scheme S2) For the abstraction at the allylic carbon this pathway is

considerably more thermodynamically favourable (∆r Ηο298 = 801 kJmol) despite having

to overcome a barrier with ∆HDagger = 895 kJmol Abstraction of the vinyl chlorine is harder by

comparison (∆r Ηο298 = 1739 kJmol ∆HDagger = 2362 kJmol) but still requires less energy

than C-Cl bond scission Our relax scan confirms that scheme Cl abstraction by Cl gives a

genuine transition state Even though Cl prefers to abstract H with an activation enthalpy of

00 kJmol and exothermicity of -667 kJmol we propose that further formation of IM1 (after

initial decomposition by unimolecular C-Cl scission) would rather proceed via Cl abstracting

Cl due to comparatively lower reaction enthalpies In addition we found that HO2 abstracting

chlorine to form 13-D derived radicals require significantly higher reaction enthalpies than

Cl abstracting Cl (Scheme S3) However OH abstracting Cl and Cl abstracting Cl from 13-D

are thermodynamically competitive with each other Abstraction with OH also appears more

kinetically favourable This is in agreement with the findings of Wilk et al [1] who showed

that OH abstracting H from propene was found to be a more dominant reaction than HO2

abstraction reactions

3

Scheme S1 ∆r Ηο298 (kJmol) for (a) allylic C-Cl and (b) vinylic C-Cl bond scission in 13-

D

Scheme S2 ∆r Ηο298 (kJmol) for (a) allylic Cl and (b) vinylic Cl abstraction from 13-

dichloroprene by Cl

(a)

(b)

+Cl Cl CH2Cl

Cl

R1 IM1

25732785

+Cl Cl HCCl

Cl

R1 IM16

37733835

(a)

(b)

+ +Cl Cl Cl CH2Cl

Cl Cl

R1 IM1

TS1895923

801832

+ +Cl Cl Cl HCCl

Cl Cl

R1 IM16

TS223622350

17391848

4

Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))

abstraction from 13-dichloroprene by OH and OOH

Scission of the allylic and vinylic C-H bonds by comparison require significantly higher

energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17

IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to

dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-

C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission

of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =

5862 kJmol (scheme S5(b))

+ +ClCl

OHCl

CH2 ClOH

+ +ClCl

OHCl

HC ClOH

+ +ClCl

HO

O ClCH2 Cl

O

OH

+ +ClCl

HO

OHC

Cl

ClO

OH

R1

R1

R1

R1

IM1

IM1

IM16

IM16

449749

16491799

14761744

26752794

584998

TS(a)

(b)

(c)

(d)

5

Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)

carbons

Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated

radical (b)

Cyclization of perchlorohexatrienes

Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)

The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4

initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23

While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713

(a)

(b)

(c)

+Cl Cl Cl ClCH

R1 IM17

44974475

+Cl ClC

Cl ClH

R1 IM18

44894479

+Cl ClCH

ClClH

R1 IM19

33973477

(a)

(b)

+Cl Cl CHClH2C

Cl

R1 IM20 IM21

39904175

+ClCH2

CHClCH2

IM1 IM20 IM22

58625717

6

kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form

IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)

However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then

formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is

exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol

Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-

elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the

formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was

produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules

out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15

has previously been observed in thermal decomposition experiments [4] However based on

the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =

264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation

of both IM15 and chlorobenzene (P1)

Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal

decomposition process These polychlorinated benzenes are potentially formed via successive

chlorination of monochlorobenzene at temperatures higher than 773 K This would require

either successive H abstraction by Cl atoms followed by addition of the latter to the vacant

radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In

either case the reaction enthalpies of these processes are favorable (for example 12-

dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)

and subsequent H elimination (∆r Ηο298 = 1052 kJmol))

Benzene was never observed in our combustion experiments and this can be attributed to

the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger

= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

3

Scheme S1 ∆r Ηο298 (kJmol) for (a) allylic C-Cl and (b) vinylic C-Cl bond scission in 13-

D

Scheme S2 ∆r Ηο298 (kJmol) for (a) allylic Cl and (b) vinylic Cl abstraction from 13-

dichloroprene by Cl

(a)

(b)

+Cl Cl CH2Cl

Cl

R1 IM1

25732785

+Cl Cl HCCl

Cl

R1 IM16

37733835

(a)

(b)

+ +Cl Cl Cl CH2Cl

Cl Cl

R1 IM1

TS1895923

801832

+ +Cl Cl Cl HCCl

Cl Cl

R1 IM16

TS223622350

17391848

4

Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))

abstraction from 13-dichloroprene by OH and OOH

Scission of the allylic and vinylic C-H bonds by comparison require significantly higher

energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17

IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to

dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-

C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission

of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =

5862 kJmol (scheme S5(b))

+ +ClCl

OHCl

CH2 ClOH

+ +ClCl

OHCl

HC ClOH

+ +ClCl

HO

O ClCH2 Cl

O

OH

+ +ClCl

HO

OHC

Cl

ClO

OH

R1

R1

R1

R1

IM1

IM1

IM16

IM16

449749

16491799

14761744

26752794

584998

TS(a)

(b)

(c)

(d)

5

Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)

carbons

Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated

radical (b)

Cyclization of perchlorohexatrienes

Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)

The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4

initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23

While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713

(a)

(b)

(c)

+Cl Cl Cl ClCH

R1 IM17

44974475

+Cl ClC

Cl ClH

R1 IM18

44894479

+Cl ClCH

ClClH

R1 IM19

33973477

(a)

(b)

+Cl Cl CHClH2C

Cl

R1 IM20 IM21

39904175

+ClCH2

CHClCH2

IM1 IM20 IM22

58625717

6

kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form

IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)

However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then

formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is

exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol

Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-

elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the

formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was

produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules

out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15

has previously been observed in thermal decomposition experiments [4] However based on

the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =

264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation

of both IM15 and chlorobenzene (P1)

Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal

decomposition process These polychlorinated benzenes are potentially formed via successive

chlorination of monochlorobenzene at temperatures higher than 773 K This would require

either successive H abstraction by Cl atoms followed by addition of the latter to the vacant

radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In

either case the reaction enthalpies of these processes are favorable (for example 12-

dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)

and subsequent H elimination (∆r Ηο298 = 1052 kJmol))

Benzene was never observed in our combustion experiments and this can be attributed to

the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger

= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

4

Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))

abstraction from 13-dichloroprene by OH and OOH

Scission of the allylic and vinylic C-H bonds by comparison require significantly higher

energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17

IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to

dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-

C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission

of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =

5862 kJmol (scheme S5(b))

+ +ClCl

OHCl

CH2 ClOH

+ +ClCl

OHCl

HC ClOH

+ +ClCl

HO

O ClCH2 Cl

O

OH

+ +ClCl

HO

OHC

Cl

ClO

OH

R1

R1

R1

R1

IM1

IM1

IM16

IM16

449749

16491799

14761744

26752794

584998

TS(a)

(b)

(c)

(d)

5

Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)

carbons

Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated

radical (b)

Cyclization of perchlorohexatrienes

Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)

The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4

initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23

While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713

(a)

(b)

(c)

+Cl Cl Cl ClCH

R1 IM17

44974475

+Cl ClC

Cl ClH

R1 IM18

44894479

+Cl ClCH

ClClH

R1 IM19

33973477

(a)

(b)

+Cl Cl CHClH2C

Cl

R1 IM20 IM21

39904175

+ClCH2

CHClCH2

IM1 IM20 IM22

58625717

6

kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form

IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)

However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then

formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is

exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol

Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-

elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the

formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was

produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules

out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15

has previously been observed in thermal decomposition experiments [4] However based on

the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =

264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation

of both IM15 and chlorobenzene (P1)

Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal

decomposition process These polychlorinated benzenes are potentially formed via successive

chlorination of monochlorobenzene at temperatures higher than 773 K This would require

either successive H abstraction by Cl atoms followed by addition of the latter to the vacant

radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In

either case the reaction enthalpies of these processes are favorable (for example 12-

dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)

and subsequent H elimination (∆r Ηο298 = 1052 kJmol))

Benzene was never observed in our combustion experiments and this can be attributed to

the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger

= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

5

Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)

carbons

Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated

radical (b)

Cyclization of perchlorohexatrienes

Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)

The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4

initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23

While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713

(a)

(b)

(c)

+Cl Cl Cl ClCH

R1 IM17

44974475

+Cl ClC

Cl ClH

R1 IM18

44894479

+Cl ClCH

ClClH

R1 IM19

33973477

(a)

(b)

+Cl Cl CHClH2C

Cl

R1 IM20 IM21

39904175

+ClCH2

CHClCH2

IM1 IM20 IM22

58625717

6

kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form

IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)

However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then

formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is

exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol

Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-

elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the

formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was

produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules

out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15

has previously been observed in thermal decomposition experiments [4] However based on

the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =

264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation

of both IM15 and chlorobenzene (P1)

Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal

decomposition process These polychlorinated benzenes are potentially formed via successive

chlorination of monochlorobenzene at temperatures higher than 773 K This would require

either successive H abstraction by Cl atoms followed by addition of the latter to the vacant

radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In

either case the reaction enthalpies of these processes are favorable (for example 12-

dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)

and subsequent H elimination (∆r Ηο298 = 1052 kJmol))

Benzene was never observed in our combustion experiments and this can be attributed to

the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger

= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

6

kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form

IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)

However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then

formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is

exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol

Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-

elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the

formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was

produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules

out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15

has previously been observed in thermal decomposition experiments [4] However based on

the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =

264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation

of both IM15 and chlorobenzene (P1)

Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal

decomposition process These polychlorinated benzenes are potentially formed via successive

chlorination of monochlorobenzene at temperatures higher than 773 K This would require

either successive H abstraction by Cl atoms followed by addition of the latter to the vacant

radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In

either case the reaction enthalpies of these processes are favorable (for example 12-

dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)

and subsequent H elimination (∆r Ηο298 = 1052 kJmol))

Benzene was never observed in our combustion experiments and this can be attributed to

the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger

= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

7

chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination

from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =

1158 kJmol Figure S2(c))

Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to

chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal

contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

-461-734

IM15

IM24

Cl

Cl

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

501395 473

358

IM25

25722491

P1+HCl

-1386-929

697792

Cl

ClH+

IM4IM23

8268

37134274

337264

236174

Cl

Cl

0

TS17

TS18

TS19

TS20

TS14

HCl

Cl

H

Cl

Cl

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

8

Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene

(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to

chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

An alternative pathway of polychlorinated benzenes is successive elimination of Cl from

hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has

been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was

not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy

surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low

levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash

1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene

hexachloropropene and hexachlorobutadiene The cyclization pathway for

Reaction coordinate

Rel

ativ

e en

thal

pyy

(kJ

mol

)

IM15

P1+HCl

-925-929

11581526

Cl

ClH+

0

TS14

(c)

HCl

Cl

H

P2+Cl2

26102610

IM26

120431

ClCl+

TS21

0

(a)

HCl

Cl

H

C

Cl

38003926

P1

+

P3+Cl

0

(b)

Cl

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

9

hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene

(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier

for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are

larger This is due to the increased electrostatic repulsion between individual Cl atoms which

actually changes the nature of the cyclisation pathway itself

Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to

hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and

thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

25862696

TS25 2068

-357-647

IM31

IM29

Rel

ativ

e en

thal

py (k

Jm

ol)

Reaction coordinate

839841

1721

IM30

P4+Cl2

-726-540

+

IM27

IM28

17-13

5503

0

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

ClCl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl

Cl

521545

25633256

TS22

TS23

TS24TS13

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

10

Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming

chlorobenzene

1787deg

12

34

TS17

12

34

TS18

1012deg

6

5

4

3

911deg

TS19 TS20

16

2550 Aring

1

6

1174 Aring

1992 Aring2585 Aring

TS21

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

11

Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming

hexachlorobenzene

1799deg

12

34

TS23

12

34

929deg

TS24

6

5

43

TS25

927deg

6 1

3026 Aring

TS26

TS27

1

6

3620 Aring2838 Aring

1905 Aring

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

12

Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM5) forming chlorobenzene

1797deg

12

3

TS5

12

31014deg

TS6

TS76

5

4

3

914deg

TS8

16

44

1

6

2816 Aring

TS9

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

13

Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived

radical(IM6) forming chlorobenzene

Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range

of 300-2000 K and pressure of 1 atm

Reaction Log A Ea (kJmol) T (K) k (s-1)

IM4rarrIM23 1431 4326 873 26 times10-12

IM5rarrIM7 1319 1763 873 4455

IM13rarrIM14 1071 38 873 30 times1010

00deg

1

2

34

TS11

TS12

6

5

4 3455deg

1

23

4

TS10

1658deg

16

TS13

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

14

Computational Kinetic and Thermodynamic Benchmarks

To provide a benchmark of accuracy of our computations we calculated the

thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic

parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine

abstraction reaction of ethylene and then compared the results with their respective

experimental values Table S2 compares the predicted and experimental standard enthalpy

change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the

calculated and experimental reaction rate parameters As illustrated our calculated

thermokinetic parameters remain in good agreement with the corresponding experimental

values For example the rate constant for the unimolecular decomposition of chloroethane

was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational

calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate

of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15

cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105

times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In

either case we find a good agreement between the experimental values and our calculated

data

Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ

(kJmol) values for dehydrohalogenation of chloroethane

∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

15

Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and

chlorine abstraction from acetylene and chloroethane

a Experimental value

T

(K) P

(atm) log A (s-1)

Ea (kJmol)

k

C2H5Clrarr C2H4+HCl

This work

1000 700 1379 2376 244 (s-1)

Ref [5]a 1384 2420

(plusmn484) 158 (s-1)

C2H5Clrarr C2H4+HCl

This work 772 016

1423 2350 214 times10-2 (s-1)

Ref [6]a 1400 2280 (plusmn831)

400 times10-2 (s-1)

C2H4+Clrarr C2H3+HCl

This work 625 100

-986 6126 105times10-15

(cm3molecules)

Ref [6]a -970 5571 439times10-15

(cm3molecules)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

16

Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K

13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0

Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0

12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0

13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0

14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033

123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0

124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0

135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0

1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0

1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0

Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0

Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003

Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087

Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0

2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0

HCl 382 1189 2294 2315 4665 4948 4959 4968 4999

CO 006 168 459 486 1078 1060 1161 762 533

CO2 025 251 870 857 2633 2839 2845 3149 3400

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

17

Table S5 mz of selected products

Retention

time

Product Identified Ions (mz)

2768 13-dichloropropene 1099684 (6 ) 749998 (100 )

4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )

6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )

8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )

11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )

13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )

15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )

9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )

7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )

11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

18

Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

19

Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

20

Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)

TS1

X Y Z

C -150534100 128529000 005141700

H -157664100 235253600 -010499000

C -039541900 055233000 006083300

H -047868000 -052169400 020015300

C 093566300 114035700 -007635200

H 098845500 221794500 -021220800

C 206778900 041794500 -003144300

H 201238000 -065796300 010462100

C 338859600 101350700 -015124400

H 344023600 209084300 -028086200

C 455502400 036617800 -011500200

H 551165400 085932400 -020781300

Cl -340674200 029329500 024459100

Cl 469580900 -135066200 008008400

Cl -506408300 -100114000 -020280100

TS2

X Y Z

C -310964700 -092749500 041819300

C -198361900 -100546200 115211400

C -070892200 -055704000 070769400

C 050314700 -104639000 049559100

C 169083900 -026579500 017614600

C 286146100 -086394600 -003218900

H -407597700 -123549400 079280700

H -208494800 -135294600 217732000

H -078753700 081154200 047033400

H 062130300 -213141200 053436400

H 160162800 081376600 011732200

H 300608000 -193586100 001529900

Cl -313781600 -034262000 -119054300

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

21

Cl 430468500 000644100 -040589900

Cl -080217000 227895500 032510500

TS3

X Y Z

C 327788200 072540900 000402400

C 201936500 116649100 001819300

C 080317500 039771300 001976700

C -045664400 083530900 -000372500

C -163155500 -001877900 000889600

C -286447800 048492600 -001708300

H 412740300 139279100 000548400

H 189706900 225000500 003101100

H 087457900 -103812900 008399000

H -063147900 191369800 -003757000

H -148455000 -109312400 003890100

H -308048600 154516100 -004731200

Cl 372882200 -094364300 -001988700

Cl -428170400 -050440600 -000364000

H 080998900 -189998600 014503900

TS4

X Y Z

C 267617000 073450300 -002458900

H 288291700 179443000 002412100

C 148035300 015255500 -000006400

H 142550300 -093198300 -002534800

C 023488200 091706100 002653800

H 032047800 200085100 004914600

C -098072500 034457100 001387400

H -106350200 -073791900 -000901500

C -221461600 111334400 002280500

H -212776400 219607400 003928100

C -345459100 062019600 000978500

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

22

H -434032000 123857800 001592400

Cl 443530500 -050717200 -004423000

Cl -381436300 -107551800 -001335900

H 589785300 -194768700 059480900

TS5

X Y Z

C 171925900 052976800 020424500

C 046493100 010397900 -017694300

C -067799200 086326600 000007800

C -201630700 041209600 -041192600

C -288025000 -027031400 042975700

C -413311100 -070297200 008244200

H 191461400 148616400 066871700

H 037406400 -087738400 -063443000

H -058370700 184783700 045619700

H -234709200 063982600 -142361200

H -253551200 -048359100 144053500

H -473626500 -065582000 -081240900

Cl 312086600 -044541000 -002711300

TS6

X Y Z

C 135032500 029863900 -043055900

C 042064500 062911200 045310800

C -082320100 133957100 006281000

C -201202400 074681800 -008853500

C -224358200 -069262100 008098500

C -342181900 -126231900 -005379100

H 127633600 049917500 -149136900

H 057467000 038761700 150228500

H -075123200 241413100 -008058900

H -287351100 135163500 -035535600

H -137739500 -130522300 032829200

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

23

H -442478800 -093759400 -029208500

Cl 282081500 -051558600 001439500

TS7

X Y Z

C -092107200 -008415700 -016132000

C -038067800 107817700 019928600

C 103188500 146387200 010276900

C 210328400 071248600 -017363600

C 211403300 -075134200 -045444600

C 227888500 -165666800 047799900

H -038509600 -092773800 -056764400

H -104971900 183870700 058952000

H 121521600 251717600 029281300

H 307258100 120281700 -020432000

H 200687800 -106078800 -149635100

H 240948100 -165014800 155084200

Cl -262513900 -038201400 -000639900

TS8

X Y Z

C -072448300 018865300 -036503600

C -003180400 118847600 022459800

C 137941600 135559200 -001414000

C 225230500 032560200 -013565500

C 193799700 -107796500 010726700

C 073462000 -162723300 005715200

H -042844000 -026472700 -129921100

H -053051500 184015300 093520700

H 177843700 236497200 001359500

H 330284900 056393900 -026151600

H 278010900 -169269900 043244700

H 034109700 -261287200 026114300

Cl -238422600 -013632500 003960100

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

24

TS9

X Y Z

C -014612600 034858400 063080400

C -152290300 086188000 084227200

C -259999600 019995500 034745600

C -240503400 -101721300 -035218400

C -115369200 -161554600 -049249100

C -005900800 -103964200 011087400

H 057146100 050084400 144082900

H -162045000 183266800 131428300

H -359818400 060273300 045673700

H -327668400 -153112000 -074532500

H -107024200 -259102800 -095415000

H 088857500 -155080100 025363000

Cl 039657100 150666500 -067256400

Cl 286378600 -054733600 018512900

TS10

X Y Z

C 294240300 -051455600 006590500

C 195598300 036794300 -010624000

C 058095500 -001426100 -006539500

C -060099400 057441000 003006600

C -187092600 -013317300 -003683000

C -303726200 050002400 007355400

H 277498400 -156714300 025055400

H 219541000 141294600 -030350800

H -063909700 165728700 017838500

H -184640700 -120788100 -018281000

H -313107700 156789700 022189500

Cl 460873800 -006645900 001349900

Cl -456019500 -031856600 -000943300

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

25

TS11

X Y Z

C -211612400 -024548900 -000016000

C -196571800 108183100 -000007600

C -070887900 176621800 -000003800

C 060994000 165711300 000001800

C 137232700 041148900 -000014300

C 270470400 041134100 000015200

H -130618400 -096018800 -000029800

H -286049200 169963800 000005500

H 119735600 257536300 000023300

H 084390000 -053438900 -000050500

H 330417800 131250500 000052100

Cl -367678600 -099398400 000009400

Cl 364406500 -104060100 -000000600

TS12

X Y Z

C 164006100 -017451100 000110400

C 167060400 115474100 -012896300

C 052651100 201721000 -015060000

C -077121200 215670800 005011200

C -173153700 107567200 034152400

C -174591700 -006803800 -033417800

H 074001400 -076602200 008257000

H 264187600 163856300 -020247200

H -118699400 316396200 002489200

H -247697200 125336300 111135400

H -108978700 -027952200 -116879400

Cl 308750100 -111857100 008157500

Cl -286157200 -135090200 000539300

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

26

TS13

X Y Z

C 063617200 086558200 042630800

C -003813100 185017100 -039414200

C -134338900 193094400 -015717300

C -226913300 105124100 023654000

C -189587600 -033978000 008590400

C -064471800 -070843800 -041671600

H 036148100 071320500 146104700

H 045158900 221382200 -129303600

H -315020200 130217000 081491400

H -244468300 -106292300 067840100

H -027919900 -037471900 -137841000

Cl 229379300 049101900 008926200

Cl -003547100 -229630600 -002851200

TS14

X Y Z

C -061025500 033623100 -009020600

C -007394900 142708900 -088981700

C 122796800 178809600 -075924300

C 202052200 120748500 027069300

C 153594600 024355700 112570300

C 022814100 -021771600 097064500

H -044679000 -060651100 -077040100

H -072306800 187306000 -163401900

H 165802300 254231600 -140489800

H 304099600 155375300 039353400

H 215762100 -016810000 190925400

H -022330900 -089661500 168030100

Cl -234828900 039479000 025379300

Cl 049924800 -233634100 -048558200

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

27

TS15

X Y Z

C -212951000 016987700 046674200

H -200194000 019181800 154150200

C -137234000 091313900 -038637000

H -153952100 082364600 -145441000

C -035509700 175886000 008472200

H 009995600 247645900 -058332600

H -025198200 193909700 114753400

Cl 151151600 032325600 -002996000

Cl -335308600 -089201200 -007642900

Cl 342010900 -075373100 000980800

TS16

X Y Z

C -070711500 133438200 -030431100

H -014126600 208253200 -082134700

C -138806000 043401900 031777000

H -088813700 -044992800 071399500

C -287877700 054309600 053584800

H -309647400 050348200 160166000

H -328597000 145399700 010575900

Cl -370677100 -084619600 -022616400

Cl 183244300 041977300 -017009100

Cl 406583200 -060058000 010826000

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

28

TS17

X Y Z

C 314371200 -055058500 006480300

C 174503300 -077820200 045228600

C 081612900 -107405900 -042783900

C -059434200 -127675600 -005457500

C -153728000 -025549900 -015223500

C -287398600 -045371400 005813100

H 393297100 -123752300 034675600

H 145863200 -069240400 151748700

H 112011500 -116573500 -148454800

H -094035700 -229201900 012610800

H -119159800 074982800 -037669900

H -330848800 -142104500 027126400

Cl 369445300 106957600 -004570500

Cl -400426800 083582400 004312900

TS18

X Y Z

C 238739900 014228400 -041940800

C 161937900 075179800 047108300

C 069877800 185361800 009303400

C -061940800 170533500 -007910300

C -132772800 043834100 004984400

C -264508800 035675300 -012047500

H 239507000 038101800 -147497000

H 166986900 045024900 151496400

H 113501800 284159400 -002379300

H -121521100 257681500 -033597800

H -075662100 -045386800 028636000

H -327337500 120372800 -036459800

Cl 348649700 -113622800 000323200

Cl -352383500 -112779000 002195400

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

29

TS19

X Y Z

C -153624600 -021481200 -012312400

C -172097900 106608700 019404500

C -073456100 215143700 013365400

C 056998000 210312900 -015970800

C 134092800 088729900 -050598000

C 196238900 016439700 041352100

H -061075600 -065471200 -046138800

H -271395900 135718900 052167600

H -114455800 313075000 036099600

H 112204000 303927700 -016724200

H 140460200 059415000 -155272500

H 194461400 038955700 147184100

Cl -282747000 -136975500 -002000300

Cl 286917300 -126562300 002661500

TS20

X Y Z

C 123168000 002979400 032931000

C 143040300 112724300 -052768700

C 047456200 211321100 -054787700

C -047456600 211321500 054787200

C -143040300 112724300 052768700

C -123167400 002978800 -032930100

H 071708800 007237900 127314200

H 211999100 100273600 -135650400

H 022695300 258522000 -149493500

H -022696100 258523600 149492400

H -211999500 100274000 135650200

H -071707700 007237000 -127313100

Cl 223342700 -136951800 015690300

Cl -223342700 -136951900 -015690500

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

30

TS21

X Y Z

C 044844300 085837100 099176200

C 120173100 166084400 019380500

C 220840800 110031700 -062870000

C 249670600 -026286300 -062334800

C 177512600 -110787600 019325600

C 064092100 -059743700 095103100

H -034820000 124880900 161301400

H 102901200 272887900 017585900

H 278279100 175666400 -127282300

H 328940100 -065286300 -124809900

H 198917700 -216788500 024758000

H 040520000 -112329400 187216600

Cl -290988700 052866300 -024159200

Cl -072396000 -121680700 -022043900

TS22

X Y Z

C -288964700 009818900 -048734100

C -150811900 -026295000 -045384900

C -074573900 -016912200 065054700

C 064878000 -053997200 065470900

C 165769600 037798200 029995800

C 292649300 014056600 -015545300

Cl -409336000 -099548800 -001895600

Cl -080098900 -079908000 -196040800

Cl -145707800 037942400 214227300

Cl 094571300 -218484100 106593400

Cl 116154500 205440200 044444700

Cl 345558000 -139210200 -070042100

Cl -334732200 168695100 -085445600

Cl 410433500 137613500 -029790800

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

31

TS23

X Y Z

C 244213800 -043443400 -053526900

C 174116500 008958400 047034500

C 067988300 109387600 025790400

C -065119400 092231800 009235300

C -138883000 -036426900 009739500

C -271807800 -059811200 -001909900

Cl 204765900 -007438500 -217160500

Cl 213718100 -024018200 212126000

Cl 137209500 269003500 027494700

Cl -157730100 236554500 -016169900

Cl -040887900 -178889300 030798100

Cl -399242900 053935800 -020630500

Cl 373376100 -153712000 -031580000

Cl -334917500 -220458000 002288300

TS24

X Y Z

C -164476500 -132154600 -009089900

C -181510700 001883400 -001108800

C -085005800 117325300 -005822900

C 048398400 123473700 -027098600

C 148399400 017315200 -046564600

C 215559600 -036410800 055300300

Cl -018682500 -219524800 -030238100

Cl -348711500 049888000 015646000

Cl -160625800 272169700 020634200

Cl 129854800 277640000 -036538700

Cl 187907700 -018914400 -210932400

Cl 337957400 -154421300 035365400

Cl -297742300 -241705700 -000035400

Cl 176619500 002598300 218234700

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

32

TS25

X Y Z

C 105780400 077003400 -108192700

C 153141400 -036002000 -037626900

C 070413100 -134292800 015550500

C -070386900 -134311700 -015522700

C -153137800 -036026600 037629800

C -105801900 076995200 108184800

Cl 199332600 220222900 -116593700

Cl 315978000 -028728300 021010500

Cl 117852700 -228531400 151800400

Cl -117788000 -228564800 -151779200

Cl -315966400 -028786100 -021031700

Cl 019615000 070046100 224501000

Cl -019633300 070024800 -224508600

Cl -199393500 220187800 116593200

TS26

X Y Z

C 093290900 -017933100 -080981400

C 058638700 113902900 -067151800

C -071608700 147843200 -021812200

C -171001300 049719000 000383400

C -139822200 -083705000 -013056100

C 000948500 -124619700 -032229600

Cl 246211800 -063776700 -134307500

Cl 171407500 237402600 -103286900

Cl -109201400 310955800 003864900

Cl -330350400 097608100 043122200

Cl -257941300 -203910600 007010700

Cl 020268300 -278042500 -115241200

Cl 283526600 011358500 225614900

Cl 057097900 -141668200 149051400

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)

33

References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)