Reaktionsprodukte yon Oxylsäuremethylester-N-methylamiden...

This work has been digitalized and published in 2013 by Verlag Zeitschrift für Naturforschung in cooperation with the Max Planck Society for the Advancement of Science under a Creative Commons Attribution4.0 International License.

Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschungin Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung derWissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht:Creative Commons Namensnennung 4.0 Lizenz.

Reaktionsprodukte yon Oxylsäuremethylester-N-methylamiden mit Antimon(V)-chlorid. Molekülspektren und Struktur

R e a c t i o n P r o d u c t s o f O x a l i c A c i d M e t h y l e s t e r - N - m e t h y l a m i d e s a n d A n t i m o n y ( V ) C h l o r i d e .

M o l e c u l a r S p e c t r a a n d S t r u c t u r e

M . R ö s s l e r [1] , W . S c h w a r z u n d A . S c h m i d t

Institut für Anorganische Chemie der Universität Stuttgart

Z . Naturforsch. 34b , 398-405 (1978); eingegangen am 9. Oktober/5. Dezember 1978

Oxal ic Ac id Methylester-N-methylamides, A n t i m o n y ( V ) Chloride

Oxalic acid dimethylester and the oxalic acid methylester-N-methylamides 2 and 4, resp., react with ant imony(V) chloride to yield the 1 : 1 addit ion c o m p o u n d 5 or the cycl ic tetrachloroant imony(V) compounds 1, 3 and 6, resp., which represent Sb02C2 and SbONC2 five ring systems, resp. Li oxalic acid methylester-N-methyl imide (9) and anti-m o n y ^ ) chloride gives the bicycl ic oc tachloro -N-methylamido o x a l a t o - 0 , 0 ' - 0 , N -d iant imony(V) (10). The crystal and molecular structure of tetrachloro-N-methylamino o x a l a t o - 0 , 0 ' - a n t i m o n y ( V ) (3) is determined b y X - r a y analysis. The vibrational and i H N M R spectra o f 2 - 1 0 are reported and discussed.

P h o s p h o r s ä u r e a l k y l e s t e r b i l d e n m i t A n t i m o n ( V ) -

c h l o r i d 1 : 1 - A d d i t i o n s v e r b i n d u n g e n , d i e u n t e r mi l-

d e n B e d i n g u n g e n A l k y l c h l o r i d a b s p a l t e n u n d d a b e i

i n r i n g f ö r m i g e T e t r a c h l o r o a n t i m o n ( V ) - p h o s p h a t e

ü b e r g e h e n [2], W ä h r e n d M o n o c a r b o n s ä u r e e s t e r m i t

d i e s e r L e w i s - S ä u r e a u c h b e i h ö h e r e n T e m p e r a t u r e n

n i c h t u n t e r A l k y l c h l o r i d e l i m i n i e r u n g [3, 4] reag ie-

r e n , s o l l s i c h O x a l s ä u r e d i m e t h y l e s t e r m i t A n t i -

m o n ( V ) - c h l o r i d g l a t t n a c h G l . ( l a ) u m s e t z e n [4],

w a s a l l e r d i n g s n i c h t m i t u n s e r e n b i s h e r i g e n E r f a h -

r u n g e n i n Ü b e r e i n s t i m m u n g z u b r i n g e n w a r . E i g e n e

U n t e r s u c h u n g e n z e i g t e n , d a ß i n d i e s e m F a l l e be-

r e i t s b e i T e m p e r a t u r e n u m 0 °C d i e B i l d u n g d e s

O k t a c h l o r o - o x a l a t o - O . O ' - d i - a n t i m o n ( V ) (1) (Gl .

( l b ) ) [4, 5] e r f o l g t .

/ > Cl4SbCH2OCOCOOCH2SbCl4 • 2HCI ( l a )

(CH3OCO)2 • 2 Sb C l5

( C l ^ b C ^ C ^ + 2CH3Cl

1

I n d i e s e m Z u s a m m e n h a n g i n t e r e s s i e r t e u n s d i e

U m s e t z u n g v o n O x a l s ä u r e m e t h y l e s t e r - N - m e t h y l -

a m i d e n , d i e i m F a l l e d e s N - M e t h y l a m i d s (2) b e i

R a u m t e m p . s o f o r t n a c h G l . (2) a b l ä u f t , w ä h r e n d

b e i E i n s a t z d e s N . N - D i m e t h y l a m i d s (4) (Gl . (3))

e i n 1 : 1 - A d d u k t 5 i s o l i e r t w e r d e n k a n n , d a s e r s t

b e i e r h ö h t e r T e m p e r a t u r e b e n f a l l s e i n e c y c l i s c h e

Sonderdruckanforderungen an Prof . Dr . A . Schmidt, Institut für Anorganische Chemie, Pfaffenwaldring 55, D-7000 Stuttgart 80. 0340-5087/79/0300-0398/$ 01.00/0

V e r b i n d u n g (Gl . (4)) l i e f e r t . I n 3 l i e g t , w i e d i e R ö n t -

g e n s t r u k t u r a n a l y s e z e i g t , e i n f ü n f g l i e d r i g e r R i n g

m i t 0 . 0 ' - V e r k n ü p f u n g v o r .

o o - II II

H,C 0C-CNHCH, + SbCL

0 ^ 0 CL Sb I + CH,Cl

X -C /H 3 C H,

0 0 II II

H,C0C-CN(CH,), • SbCL

(2)

H.C0C-C 9 .0 -»• SbCL S 5

VN(CH3)2 ( 3 )

70 C i.Vak.

Hb) 80°C in 1,2-C2H4Cl2

0 ^ 0 CL Sb I • C H,Cl

X ^ r ^ O ^ ^ N I C H , ^

U)

W i e a u s s p e k t r o s k o p i s c h e n U n t e r s u c h u n g e n z u

e n t n e h m e n is t , i s t d ie L e w i s - S ä u r e i n 5 a n d a s C a r -

b o n y l s a u e r s t o f f a t o m d e r S ä u r e a m i d g r u p p i e r u n g ge-

b u n d e n .

W i r d 4 m i t 2 m o l A n t i m o n ( V ) - c h l o r i d u m g e s e t z t ,

d a n n w i r d a u c h i n d i e s e m F a l l e b e r e i t s b e i R a u m -

t e m p . M e t h } d c h l o r i d a b g e s p a l t e n u n d es e n t s t e h t

d a s 1 : 1 - A d d u k t a u s 6 u n d A n t i m o n ( V ) - c h l o r i d (8),

d a s a u c h n a c h G l . (5) z u g ä n g l i c h is t . A u s 3 e n t s t e h t

a n a l o g 7 :

M. Rössler et al. • Chloroantimon(V)-Verbindungen 399

3, 6 • sbci , 0 ^ 0 - S b C 5

CI<Sb I

X o ^ N C R 1 5 ' CH, R

H 7 C H 3 8

A n a l o g G l . (6) [6] h a b e n w i r v e r s u c h t , a u s 7

C h l o r w a s s e r s t o f f a b z u s p a l t e n , u m d i e n o c h u n b e -

k a n n t e V e r b i n d u n g 10 m i t O . N - u n d O . O ' - V e r -

CH,

Cl, Sb' N ^ 0 - S b C l 5

V I V S < H

CH,

200°C i.Vak.

80 'C in 1,2-C2H^C!2

C H 3

Cl<Sb | SbCl4

V S * / i CH,

(6)

k n ü p f u n g z u e r h a l t e n . 1 0 w a r j e d o c h n a c h d i e s e m

V e r f a h r e n n i c h t z u g ä n g l i c h u n d k o n n t e n u r ü b e r

d e n W e g G l . (7) d a r g e s t e l l t w e r d e n , w o b e i 9 a u s 2

u n d L i t h i u m b u t y l e r h a l t e n w u r d e .

o o » I I

CH,0C -CNCH, Li + 2 SbCL

CI4Sb I SbCI + 2 LiSbCI

I CH,

10 3

Strukturbest immung des Tet rach loro -N-methy laminooxa la to -O .O ' -ant imon(V) ( 3 )

E i n k r i s t a l l e v o n 3 w u r d e n d u r c h U m k r i s t a l l i s i e -

r e n a u s D i c h l o r m e t h a n e r h a l t e n . D i e B e s t i m m u n g

d e r G i t t e r k o n s t a n t e n ( T a b . I ) e r f o l g t e bei e t w a

— 1 0 0 °C d u r c h O p t i m i e r u n g v o n 2 5 a u s g e w ä h l t e n

R e f l e x e n a n e i n e m a u t o m a t i s c h e n E i n k r i s t a l l d i f -

f r a k t o m e t e r S y n t e x P 2 i u n d a n s c h l i e ß e n d e r V e r -

f e i n e r u n g d e r M e ß w e r t e .

B e i d e r n a c h f o l g e n d e n M e s s u n g k o n n t e n b is 26 — 70° 2 6 5 5 u n a b h ä n g i g e R e f l e x e e r f a ß t w e r d e n , v o n

d e n e n 128 e ine I n t e n s i t ä t I < 2ct(I) h a t t e n ( M o K a -

S t r a h l u n g , co-scan, G r a p h i t m o n o c h r o m a t o r ) .

S y s t e m a t i s c h e A u s l ö s c h u n g e n (MX): h — 2 n 1 ; OkO: k = 2 w + 1 u n d 001: l = 2n-\-1) e r g e b e n ein-

d e u t i g d ie R a u m g r u p p e P 2 i 2 i 2 i [7]. E i n e r dre id i -

m e n s i o n a l e n P a t t e r s o n s y n t h e s e k o n n t e d i e L a g e

des A n t i m o n s e n t n o m m e n w e r d e n , d u r c h s ich d a r a n

a n s c h l i e ß e n d e F o u r i e r - u n d D i f f e r e n z - F o u r i e r - S y n -

t h e s e n w u r d e n die O r t s p a r a m e t e r d e r r e s t l i c h e n

A t o m e e r m i t t e l t ; d ie W a s s e r s t o f f a t o m e b l i e b e n u n -

b e r ü c k s i c h t i g t .

D i e V e r f e i n e r u n g e n , j e w e i l s m i t v o l l e r M a t r i x ,

bei d e r d ie F o - W e r t e m i t G e w i c h t e n v e r s e h e n w a -

ren, die d e r S t a n d a r d a b w e i c h u n g a u f g r u n d d e s s ta-

t i s t i s c h e n F e h l e r s d e r M e s s u n g a n g e p a ß t w a r e n ,

k o n v e r g i e r t e m i t a n i s o t r o p e n T e m p e r a t u r f a k t o r e n

be i e i n e m Ä - W e r t v o n 0,046 (R = ||F0| — |F0||/|FC|).

(Die T a b e l l e n d e r b e o b a c h t e t e n u n d b e r e c h n e t e n

S t r u k t u r f a k t o r e n s o w i e d e r a n i s o t r o p e n T e m p e r a -

t u r p a r a m e t e r s i n d a u f A n f r a g e v o n d e n A u t o r e n z u

e r h a l t e n . ) A u f e ine K o r r e k t u r d e s A b s o r p t i o n s f e h -

lers w u r d e v e r z i c h t e t .

D i e E r g e b n i s s e d e r V e r f e i n e r u n g e n s ind in d e n

T a b e l l e n II—III z u s a m m e n g e s t e l l t , d ie M o l e k ü l -

s t r u k t u r z e i g t A b b . 1 , d i e B e z e i c h n u n g d e r A t o m e

in d e r A b b . 1 s t i m m t m i t d e r i n d e n T a b e l l e n ü b e r -

ein.

Tab. I I . Ortsparameter und isotrope Temperaturpara-meter (in pm 2 ) von 3.

A t o m x/a(a) y/b (<r) z/c(a) U(ir)

Sb .1196 .1148 .3121 205(1) C l l .3141 .0130 .1681 399(9) C12 .3262 .2982 .2613 374(9) C13 .1036 .1967 .4687 262(6) C14 —.0882 .1331 .2418 337(8) O l .4441 .0707 .3855 228(16) 0 2 .1347 —.0536 .3710 209(16) 0 3 .2553 —.2083 .4598 275(20) C l .4410 —.0341 .4298 182(19) C2 .2645 —.1078 .4210 186(16) C3 .7490 —.0159 .4926 244(23) N .5737 —.0781 .4797 177(16)

Tab . I . Kristalldaten von 3. Formelgewicht 365,63.

Elementar- orthorhombisch Raumgruppe P212x2! zelle

Raumgruppe

o [pm] 738,4(2) Z 4 b [pm] 1102,5(3) ;pröntg. [gern - 3 ] 2,283 c [pm] 1306,7(4) J^exp. [gem- 3 ] 2,25 V [pm 3 ] 1063,77 x 106 <MM0Ka [ cm- 1 ] 37,9

S ä m t l i c h e R e c h n u n g e n z u r S t r u k t u r b e s t i m m u n g

w u r d e n m i t d e m P r o g r a m m s y s t e m , , X T L / E - X T L "

[8] a n e i n e m N o v a 1 2 0 0 - R e c h n e r d u r c h g e f ü h r t . Z u r

B e r e c h n u n g d e r A t o m f a k t o r e n v e r w e n d e t e n w i r d ie

K o e f f i z i e n t e n v o n C r o m e r u n d W a b e r [9].

I n 3 l i e g e n , v o n d e n M e t h y l w a s s e r s t o f f a t o m e n

400 M. Rössler et al. • Chloroantimon(V)-Verbindungen 400

Tab. I I I . Bindungsabstände (in pm) und -winkel (in °) von 3. In Klammern die Standardabweichung, bezogen auf die letzten Dezimalen.

Sb C l l Sb - C 1 2 Sb - C 1 3 Sb - C 1 4 Sb - O l Sb - 0 2 Cl 1 - S b - C 1 2 Cl 1 - S b - C 1 3 Cl 1 - S b - C 1 4 Cl l - S b - 0 1 Cl l - S b - 0 2 C 1 2 - S b - C 1 3 C 1 2 - S b - C 1 4 C 1 2 - S b - 0 1 C 1 2 - S b - 0 2 C 1 3 - S b - C 1 4 C 1 3 - S b - 0 1 C 1 3 - S b - 0 2 C 1 4 - S b - 0 1 C 1 4 - S b - 0 2 O l - S b - 0 2

234,9(2) 232,4(2) 234,6(2) 232,4(2) 210,2(6) 206,7(5)

92,4(1) 172,5(1) 93,1(1) 86,9(2) 87,3(2) 92,1(1)

100,4(1) 89,2(2)

168,9(2) 92,0(1) 87,2(2) 87,2(2)

170,4(2) 90,8(2) 79,7(2)

0 1 - C l 0 2 - C 2 C 1 - C 2 C l - N C 2 - 0 3 N - C 3 S b - O l - C l S b - 0 2 - C 2 0 1 - C 1 - C 2 0 1 - C l - N C 2 - C 1 - N 0 2 - C 2 - 0 3 0 2 - C 2 - C 1 C 1 - C 2 - 0 3 C l - N - C 3

129,2(9) 130,5(9) 154,0(10) 127,3(9) 122,0(9) 147,4(10) 113,3(5) 115,3(5) 117,0(6) 123,8(7) 119,2(6) 125,7(7) 114,6(6) 119,7(6) 123,8(6)

Abb . 1. Molekülstruktur des Tetrachloro-N-methyl -aminooxalato-O.O' -antimon(V) (3). Zur Darstellung der Schwingungsellipsoide ( 5 0 % Wahrscheinlichkeit) wurde das Programm Ortep [10] verwendet.

s o w i e C l ( l ) u n d Cl(3) a b g e s e h e n , a l le A t o m e inner-

h a l b d e r F e h l e r g r e n z e n in e i n e r E b e n e . C l ( l ) u n d

Cl(3) s t e h e n s e n k r e c h t d a z u . D i e E i n z e l m o l e k ü l e

s ind ü b e r H - B r ü c k e n b i n d u n g e n , die z w i s c h e n d e m

P r o t o n d e r A m i d - G r u p p i e r u n g u n d d e m 0 ( 3 ) - A t o m

v e r s c h i e d e n e r M o l e k e l n a u s g e b i l d e t s ind, z u Z i c k -

Z a c k - K e t t e n v e r k n ü p f t . I m G e g e n s a t z d a z u l i egt

d a s T e t r a c h l o r o - N - m e t h y l a m i n o - N ' - m e t h y l a m i d o -

o x a l a t o - O . N ' - a n t i m o n ( V ) d i m e r v o r [ 1 1 ] ,

D i e v e r g l e i c h b a r e n A b s t ä n d e des S b 0 2 C 2 - R i n g e s

v o n 3 s ind t r o t z d e r u n t e r s c h i e d l i c h e n S u b s t i t u e n -

t e n a m C ( l ) u n d C(2) n a h e z u g l e i c h , so d a ß e in

p r a k t i s c h s y m m e t r i s c h e r 5 - R i n g m i t C2v-Symme-

CH, \ V N

R c v

Cl,Sb

CH, I .

/0./N-H

( I V c - o

CH, c - 0

/ CH,

CH,

Uw NC' \ I sba4

H-N'C nC/ I CH,

C - 0 CH,

0—c

N(H)-0 287 pm Cl4Sb_ I \ C - 0

N(H)-0 282pm

Abb . 2. Verknüpfung des Tetrachloro-N-methylamino-N' -methylamidooxalato-O.N' -antimon(V) (links) bzw. des Tetrachloro -N -methylaminooxalato - 0 . 0 ' -antimon (V) (3) (rechts) über H-Brückenbindungen.

trie resu l t ier t . I n t e r e s s a n t s ind die m i t 130 p m

r e l a t i v k u r z e n C ( l ) - 0 ( 1 ) - u n d C ( 2 ) - 0 ( 2 ) - A b s t ä n d e ,

die, e b e n s o w i e d e r m i t 127 p m g e g e n ü b e r f r e i e n

S ä u r e a m i d e n [12] s t a r k v e r k ü r z t e C ( l ) - A b s t a n d ,

a u f a u s g e p r ä g t e M e h r f a c h b i n d u n g s a n t e i l e i n n e r h a l b

d e r O C O - u n d N C O - G r u p p i e r u n g e n h i n d e u t e n .

Spektroskopische Untersuchungen

V o n a l l e n hier b e s p r o c h e n e n V e r b i n d u n g e n w u r -

d e n k o m p l e t t e I R - u n d R a m a n - S p e k t r e n a u f g e -

n o m m e n . D i e M e ß w e r t e s i n d i m e x p e r i m e n t e l l e n

T e i l w i e d e r g e g e b e n .

I n T a b . I V s ind die I R - u n d R a m a n - S p e k t r e n d e r

V e r b i n d u n g 3 m i t Z u o r d n u n g s v o r s c h l ä g e n w i e d e r -

g e g e b e n . D a b e i h a b e n w i r z u r U n t e r s t ü t z u n g d e r

Z u o r d n u n g e n a u c h d a s N - d e u t e r i e r t e O x a l s ä u r e -

m e t h y l e s t e r - N - m e t h y l a m i d (3, N D s t a t t N H ) dar-

g e s t e l l t u n d in F o l g e r e a k t i o n e n u m g e s e t z t . D a die

S p e k t r e n v o n 1 sowie d e s O k t a c h l o r o b i s - ( N - m e t h y l -

a m i d o ) - O . N - O ' N ' - o x a l a t o - d i a n t i m o n ( V ) b e r e i t s aus-

f ü h r l i c h d i s k u t i e r t w u r d e n [5, 6], sol l in d i e s e r A r -

b e i t n u r a u f die w e s e n t l i c h e n O C N - u n d O C O - G e -

r ü s t s c h w i n g u n g e n u n d d e r e n Ä n d e r u n g e n einge-

g a n g e n w e r d e n .

D i e a n t i s y m m e t r i s c h e n O C O - u n d N C O - V a l e n z -

s c h w i n g u n g e n v o n 2 - 1 0 s i n d i m B e r e i c h v o n 1630

bis 1780 c m - 1 p r o b l e m l o s z u z u o r d n e n . I n 2 u n d 4,

d e n b e i d e n f r e i e n B a s e n , ist die k u r z w e l l i g e A b -

s o r p t i o n d e r O C O - V a l e n z s c h w i n g u n g z u z u s c h r e i b e n ,

w ä h r e n d die l ä n g e r w e l l i g e w e g e n d e r r e l a t i v h o h e n

B e t e i l i g u n g d e r G r e n z f o r m B a m G r u n d z u s t a n d

der M o l e k e l n d u r c h die N C O - B e w e g u n g v e r u r s a c h t

w i r d . I n b e i d e n F ä l l e n b e s i t z e n diese b e i d e n A b -

s o r p t i o n e n in erster L i n i e d e n C h a r a k t e r e i n e r Car-


Tab. IV. IR- und Ramanspektren des Tetrachloro-N-methylaminooxalato-O.O'-antimon(V) (3) und 3 (ND statt NH).

Zuordnung Cl4Sb02C20NHCH3 (3) IR fes t Rafest R a i n CII3CN

Cl4Sb02C20NDCH3 (3, ND statt NH) IRfest Ratest R a i n CH3CN

j>NH, ND vCH

vOCO as vNCO as <5NH, ND

<5CH

vNCO s rOCO s g,yCH

yNH, ND vNC vCC ZlOCO/NCO Geg. T. zlOCO/NCO Gl. T.

A Gerüst

vSbO

üst |

vSbCl2 as äq »>SbCl4 s Geg. T. KSbCl4 s Gl. T. i>SbCl2 as ax A Gerüst j <5SbCl

3300 st 3291(6) ? 2455 mst 2451(10) 1 ? 3028(20) ? ? 3022(3) ?

3022(13) 2964(59) 2960(63) 2812(7) 2878(2) 2810(8)

1743 sst 1742(85) 1760(31)tp 1750 sst 1746(98) 1761(72)tp 1694 sst 1694(66) 1702(28)tp 1690 sst 1692(81) 1700(84)tp 1510 m 1502(16) 1518(8) tp 1055 Sch 1054(25) 1057(26) tp

1049 s 1442 ss 1448(16) 1452(13) dp 1446 mst 1445(82) 1447(78) tp 1412 st 1414(25) 1416(15) dp 1413 st 1416(12) 1417(8) dp 1371 ss 1375 ss 1295 sst 1296(Sch) ? 1446 mst 1445(82) 1447(75) tp 1315 Sch 1308(48) 1310(30)tp 1270 st 1272(17) ?

1236 Sch 1237(27) ? 1230 ss 1235(5) V 1228 sm 1228(4) 1179s 1183(4) 1105 Sch 1116(12) 1157 ss 1156(2) 1157 m 1154(11) V 926 st 928(29) ? 1019 m 1020(2) ? 1049 sm 1052(25) 1057(26)tp 891 m 896(1) ? 872 ss 879(8) ? 810 Sch 809(17) 810(2) dp 807 Sch 810(20) 810(3) dp 798 mst 78S a

798(1) 800(3) tp 792 mst 792(2) 796(5) tp l 00 ö 577 s 584(59) 588(36)tp 576 sm 576(42) 576(60)tp 548 ss 545(87) 548(65)p 548 ss 545(82) 548(89)p 508 sm 506(7) 508(1) dp 507 s 507(6) 508(5) dp 418 m 414(21) 416(6) dp 411 sm 415(23) 414(30) dp 380 Sch 374 Sch 385(180) dp 380 Sch 379 Sch 381(360) dp 372 sst 366(842) 375(500)p 370 st 369(840) 375(757)p 329 s 330(1000) 335(1000)p 325 ss 331(1000) 326(1000) p 298 ss 280(206) 279(152) dp 292 ss 282(232) 276(178) dp 275 Sch 228(38) 230(12) dp 270 ss 228(44) 224(7) dp 260 ss 260 ss

(CsBr) 172(206) 171(109) dp (CsBr) 173(188) 160(82) dp 162(60) 152(91) dp 163(54) 152(89) dp 148(45) 149(277)

- < > - - < f

A B

b o n y l s c h w i n g u n g . I n d e n c y c l i s c h e n A n t i m o n v e r -

b i n d u n g e n 3 u n d 6 i s t d i e k u r z w e l l i g e B a n d e e b e n -

f a l l s v o r n e h m l i c h d u r c h d i e C a r b o n y l s c h w i n g u n g

d e r O C O - G r u p p i e r u n g b e d i n g t . W i e d i e p r a k t i s c h

g l e i c h e n B i n d u n g s a b s t ä n d e 0 ( 1 ) C ( 1 ) u n d C ( 1 ) N

s o w i e d e r 0 ( 1 ) C ( 1 ) N - B i n d u n g s w i n k e l i n 3 z e i g e n ,

m ü s s e n d i e s y m m e t r i s c h e u n d a n t i s y m m e t r i s c h e

N C O - V a l e n z s c h w i n g u n g s e h r s t a r k k o p p e l n , s o d a ß

i n 3 u n d 6 d i e l ä n g e r w e l l i g e d e r b e i d e n A b s o r p t i o n e n

e i n e n b e s o n d e r s h o h e n A n t e i l a n C N - V a l e n z s c h w i n -

g u n g b e i n h a l t e t . I n d e r A d d i t i o n s v e r b i n d u n g 5

w i r d d i e L e w i s - S ä u r e a n d a s O - A t o m d e r S ä u r e a m i d -

g r u p p i e r u n g g e b u n d e n , w a s a u s d e n ^ - N M R - D a -

t e n u n d d a r a u s h e r v o r g e h t , d a ß d i e B a n d e b e i

1 7 5 0 c m - 1 ( 4 ; j ' O C O a s ) u n v e r ä n d e r t b l e i b t , d i e A b -

s o r p t i o n b e i 1 6 6 5 c m - 1 ( 4 ; j>NCO a s ) d a g e g e n w e g e n

d e r z u n e h m e n d e n B e t e i l i g u n g v o n G r e n z f o r m B i m

A d d u k t n a c h 1 6 3 2 c m - 1 v e r s c h o b e n w i r d . D i e s e

V e r s c h i e b u n g i s t s i c h e r n i c h t a u s s c h l i e ß l i c h e i n e

F o l g e d e r L a d u n g s v e r ä n d e r u n g i n n e r h a l b d e r N C O -

G r u p p i e r u n g , s o n d e r n i n g e r i n g e r e m U m f a n g e e i n

M a s s e n e f f e k t , b e d i n g t d u r c h d a s s c h w e r e A n t i -

m o n ( V ) - c h l o r i d . B e i 7 u n d 8 w i r d A n t i m o n ( V ) -

c h l o r i d a n d e n C a r b o n y l s a u e r s t o f f a m C ( 2 ) - A t o m

a d d i e r t , w a s e b e n f a l l s z u e i n e r V e r g r ö ß e r u n g d e s

C O - B i n d u n g s a b s t a n d e s u n d d a m i t z u r b e o b a c h t e -

t e n l a n g w e l l i g e n V e r s c h i e b u n g d e r O C O - V a l e n z -

a b s o r p t i o n u m ca. 1 0 0 c m - 1 f ü h r t , s o d a ß i n d i e -

s e n b e i d e n V e r b i n d u n g e n d i e O C O - V a l e n z s c h w i n -

g u n g l ä n g e r w e l l i g g e f u n d e n w i r d a l s d i e e n t s p r e -


c h e n d e N C O - S c h w i n g u n g . I m B i c y c l u s 10 s c h l i e ß -

l i c h a b s o r b i e r e n b e i d e S c h w i n g u n g e n be i 1 6 6 5 u n d

1 6 3 1 c n r 1 r e l a t i v n a h e b e i e i n a n d e r u n d e i n e e in-

d e u t i g e Z u o r d n u n g d e r b e o b a c h t e t e n B a n d e n z u r

e i n e n o d e r a n d e r e n B e w e g u n g i s t n i c h t m ö g l i c h .

D a s L i - S a l z z e i g t w e g e n d e s B i n d u n g s a u s g l e i c h e s

i n d e r A m i d - G r u p p i e r u n g e i n e s t a r k k u r z w e l l i g v e r -

s c h o b e n e a n t i s y m m e t r i s c h e N C O - V a l e n z a b s o r p t i o n .

V o n d e n s y m m e t r i s c h e n O C O - u n d N C O - V a l e n z -

s c h w i n g u n g e n a b s o r b i e r e n d i e N C O - S c h w i n g u n g e n

i n e i n e m g r ö ß e r e n F r e q u e n z b e r e i c h z w i s c h e n 1 2 2 0

u n d 1 5 1 0 c m - 1 . D i e s i s t e i n e F o l g e d e r K o p p l u n g

d i e s e r B e w e g u n g m i t d e r N H - u n d N D - D e f o r m a -

t i o n s - b z w . N C 2 - V a l e n z s c h w i n g u n g . D a d u r c h w i r d

die L a g e d i e s e r S c h w i n g u n g e n n i c h t n u r d u r c h die

B e t e i l i g u n g d e r G r e n z f o r m e n A u n d B a m G r u n d -

z u s t a n d , s o n d e r n a u c h d u r c h K o p p l u n g s e f f e k t e

s t a r k b e e i n f l u ß t u n d d a m i t e i n w e n i g e r c h a r a k t e -

r i s t i s c h e r F r e q u e n z g a n g b e o b a c h t e t .

I n 2 o r d n e n w i r d i e O C O - S c h w i n g u n g d e r B a n d e

b e i 1 3 0 4 c m - 1 , d i e d e r N C O - S c h w i n g u n g b e i

1 2 2 4 c m - 1 z u . D i e s l e g t d a s S p e k t r u m v o n 2 ( N D

s t a t t N H ) n a h e . I n d i e s e r V e r b i n d u n g t r i t t i m G e -

g e n s a t z z u r N H - V e r b i n d u n g d i e N D - D e f o r m a t i o n s -

s c h w i n g u n g l ä n g e r w e l l i g a u f a l s d i e s y m m e t r i s c h e

N C O - V a l e n z s c h w i n g u n g . D a s b e d i n g t i n d i e s e m

F a l l e w e g e n d e r e n t g e g e n g e s e t z t e n K o p p l u n g e i n e

V e r s c h i e b u n g d e r N C O - A b s o r p t i o n n a c h k ü r z e r e n

W e l l e n z a h l e n . B e s o n d e r s a u f f a l l e n d is t d i e s e r K o p p -

l u n g s e f f e k t b e i 3 u n d 3 ( N D s t a t t N H ) . I n d i e s e n

V e r b i n d u n g e n a b s o r b i e r t d i e s y m m e t r i s c h e N C O -

V a l e n z s c h w i n g u n g m i t 1 2 7 0 u n d 1 4 4 0 c m - 1 l ä n g e r -

w e l l i g b z w . k ü r z e r w e l l i g a l s d i e s y m m e t r i s c h e O C O -

S c h w i n g u n g ( 1 3 1 5 b z w . 1 2 9 5 c m - 1 ) . E b e n f a l l s w i r d

d i e s e r E f f e k t b e i 7 u n d 10 b e o b a c h t e t . I n b e i d e n

V e r b i n d u n g e n l i e g t d i e s y m m e t r i s c h e O C O - V a l e n z -

a b s o r p t i o n m i t 1 3 4 2 b z w . 1 3 8 6 c m - 1 w e g e n d e r

B e a n s p r u c h u n g v o n L a d u n g d e r C ( 2 ) 0 - G r u p p e

d u r c h A n t i m o n k ü r z e r w e l l i g a l s i n 3. D i e s y m m e -

t r i s c h e N C O - S c h w i n g u n g a b s o r b i e r t i n 7 w e g e n

d e s K o p p l u n g s e f f e k t e s - d e r i n 10 w e g f ä l l t -

m i t 1260 c m - 1 e r h e b l i c h l ä n g e r w e l l i g a l s i n 1 0

( 1 4 3 4 c m - 1 ) .

I n 4 b e o b a c h t e t m a n d i e s y m m e t r i s c h e N C O - V a -

l e n z a b s o r p t i o n b e i 1 5 0 9 c m - 1 . W e n n d i e s e S c h w i n -

g u n g n a c h A d d i t i o n v o n A n t i m o n ( V ) - c h l o r i d i n 5

t r o t z d e r h ö h e r e n B e t e i l i g u n g d e r G r e n z f o r m B m i t

1447 c m - 1 be i t i e f e r e r F r e q u e n z a b s o r b i e r t , d a n n

k a n n d a s n u r d u r c h e i n e V e r ä n d e r u n g d e r K o p p -

l u n g s v e r h ä l t n i s s e i n d e r C - N ( C H 3 ) 2 - G r u p p e a l s

F o l g e d e r Ä n d e r u n g d e r L a d u n g s v e r t e i l u n g e r k l ä r t

w e r d e n . E r h ä r t e t w i r d d i e s e A n n a h m e d a d u r c h , d a ß

i n 6 u n d 8 d iese S c h w i n g u n g e b e n f a l l s u m 1400 c m - 1

g e f u n d e n w i r d .

I m 1 : 1 - A d d u k t 5 t r e t e n i m F e s t k ö r p e r f ü r d i e

C C - V a l e n z s c h w i n g u n g z w e i A b s o r p t i o n e n b e i 820

u n d 7 9 5 c m - 1 a u f . D a i m R a m a n - L ö s u n g s s p e k t r u m

n u r n o c h e i n e L i n i e b e i 822 c m - 1 g e f u n d e n w i r d ,

n e h m e n w i r a n , d a ß i m F e s t s t o f f v e r s c h i e d e n e K o n -

f o r m e r e v o r l i e g e n .

I n T a b . V s i n d d i e E r g e b n i s s e d e r 1 H - N M R -

U n t e r s u c h u n g e n w i e d e r g e g e b e n . I n a l l e n F ä l l e n

w e r d e n d i e N H - u n d N C H 3 ( H ) - b z w . N ( C H 3 ) 2 - P r o -

t o n e n s i g n a l e n a c h A d d i t i o n d e r L e w i s - S ä u r e n S b C l s

b z w . S b C U n a c h t i e f e m F e l d v e r s c h o b e n . I n t e r e s s a n t

i s t , d a ß die A u f s p a l t u n g d e r N ( C H 3 ) 2 - S i g n a l e i n 4

u n d 5, d i e ca. 0,03 p p m b e t r ä g t , i n 6 u n d 8, w o d i e

D r e h b a r k e i t u m d i e C C - A c h s e w e g e n d e s R i n g -

s c h l u s s e s a u f g e h o b e n is t , a u f ca. 0 , 4 5 p p m a n -

w ä c h s t .

Experimenteller Teil D i e I R - S p e k t r e n w u r d e n a l s V e r r e i b u n g e n i n

N u j o l b z w . H o s t a f l o n ö l z w i s c h e n N a C l - b z w . C s B r -S c h e i b e n m i t e i n e m I R - S p e k t r o p h o t o m e t e r P E 4 5 7 ( P e r k i n - E l m e r ) a u f g e n o m m e n . D i e R a m a n - S p e k -t r e n w u r d e n m i t e i n e m C o d e r g L a s e r - G e r ä t P H O r e g i s t r i e r t , w o b e i z u r A n r e g u n g d i e 4880 Ä - L i n i e e i n e s A r g o n - L a s e r s d i e n t e . D i e i H - N M R - S p e k t r e n w u r d e n m i t e i n e m W P 60 d e r F i r m a B r u k e r b e i 60 M H z g e g e n T M S a l s e x t e r n e m S t a n d a r d i n ge-s ä t t i g t e n C D 2 C l 2 - L ö s u n g e n v e r m e s s e n .

Tab. V. 1H-NMR-Daten (d [ppm], J [Hz], Standard TMS extern). OCH3 NCH3 NCH3(H) N(CH3)2 NH JH,H

H3COOC-CONHCH3 (2) 3,83 _ 2,87 _ 7,33 5,0 Cl4Sb02C20NHCH3 (3) - - 3,43 - 9,15 6,2 Cl4Sb02C20NHCH3 • SbCl5 (7) - - 3,49 - 9,04 5,6 Cl4Sb02C20NCH3 • SbCl4 (10) - 3,09 - - - -

CH3OOC-CON(CH3)2 (4) 3,80 - - 2,91/2,94 - -

CH3OOC-CON(CH3)2 • SbCl5 (5) 3,92 - - 3,34/3,36 - -

Cl4Sb02C20N(CH3)2 (6) - - - 3,52/3,98 - -

Cl4Sb02C20N(CH3)2 • SbCl5 (8) - - - 3,46/3,91 - -


W e g e n d e r F e u c h t i g k e i t s e m p f i n d l i c h k e i t d e r A n -t i m o n ( V ) - V e r b i n d u n g e n w u r d e n a l l e U m s e t z u n g e n i n a b s o l u t e n L ö s u n g s m i t t e l n u n t e r A u s s c h l u ß v o n L u f t f e u c h t i g k e i t d u r c h g e f ü h r t .

Oxalsäuremethylester-N-methylamid (2) w u r d e a n a -l o g [13] d a r g e s t e l l t . D a s N - d e u t e r i e r t e 2 ( N D s t a t t N H ) e r h i e l t e n w i r d u r c h v i e r m a l i g e s A u f l ö s e n v o n 2 i n D 2 O u n d a n s c h l i e ß e n d e m A b z i e h e n d e s D2O i . V a k . W i e d a s I R - S p e k t r u m z e i g t e , w a r d e r H - D -A u s t a u s c h m i n d e s t e n s z u 9 9 % e r f o l g t . A n a l y s e n a c h s t e h e n d .

IR: 3340 s t , 3005 ss, 2 9 5 5 s, 1 7 3 6 m s t , 1 6 9 4 sst , 1 5 4 3 m , 1 4 5 8 s, 1 4 5 0 S c h , 1 4 4 0 m , 1 4 1 5 m , 1 3 7 5 s, 1304 s t , 1 2 2 4 m s t , 1 1 9 1 s , 1 1 6 0 s(br) , 1058 m , 9 6 1 s m , 8 7 5 ss, 820 ss, 7 7 6 s m , 7 1 8 ss, 697 ss, 5 4 8 s, 5 0 5 s 3 5 5 s

Ra (in H20) \ 3 0 5 3 ( 6 7 ) d p , 2965(966) p , 2 9 5 5 ( S c h ) ? , 2862(100) p , 2 8 1 5 ( 8 5 ) p , 1 7 7 4 ( 2 9 2 ) p , 1 6 8 5 ( 4 9 ) t p , 1 5 5 2 ( 1 7 3 ) p , 1 4 4 5 ( 1 7 2 ) d p , 1 4 1 6 ( 4 3 ) d p , 1 3 1 4 ( 5 0 4 ) p , 1 2 3 5 ( 1 1 7 ) t p , 1 1 8 4 ( 1 7 6 ) p , 1 1 5 8 ( 1 9 4 ) p , 1 1 5 8 ( 1 9 4 ) p , 1 0 4 8 ( 1 7 2 ) p , 972(80) t p ? , 873(1000) p , 820(86) d p , 4 1 5 ( 3 1 9 ) p , 386(860) p , 3 6 2 ( 1 6 6 ) p , 295(68) d p .

Oktachloro-oxalato-O.O'-diantimon(V) (1): Zu ei-n e r L ö s u n g v o n 5 , 9 g (50,0 m m o l ) O x a l s ä u r e d i m e -t h y l e s t e r i n 5 0 m l 1 . 2 - D i c h l o r e t h a n w i r d b e i 0 °C u n t e r R ü h r e n e i n e L ö s u n g v o n 29,9 g (0,1 m o l ) A n t i m o n ( V ) - c h l o r i d i n 5 0 m l C H 2 C 1 - C H 2 C 1 ge-t r o p f t , w o b e i s i c h s o f o r t M e t h y l c h l o r i d e n t w i c k e l t . Z u r V e r v o l l s t ä n d i g u n g d e r U m s e t z u n g w u r d e n a c h b e e n d e t e r Z u g a b e 4 h a m R ü c k f l u ß e r h i t z t . I n e ine a u f — 78 °C g e k ü h l t e F a l l e k o n d e n s i e r e n d a b e i 4,4 g (87,2 m m o l ) ( 8 7 , 2 % ) C H 3 C 1 . A u s d e r L ö s u n g k r i -s t a l l i s i e r t e n i m K ü h l s c h r a n k 22,7 g ( 7 3 , 9 % ) a n a l y -s e n r e i n e s 1 . A n a l y s e n a c h s t e h e n d .

Tetrachloro - N - methylaminooxalato - 0.0' - antimon -(V) (3) bzw. (3 (ND statt NH)): 5 , 8 5 g (50,0 m m o l ) O x a l s ä u r e m e t h y l e s t e r - N - m e t h y l a m i d (2) b z w . (2 ( N D s t a t t N H ) ) g e l ö s t i n 100 m l C H 2 C 1 - C H 2 C 1 w e r -d e n b e i 0 °C u n t e r R ü h r e n m i t e i n e r L ö s u n g v o n 1 4 , 9 5 g (50,0 m m o l ) S b C l 5 i n 20 m l C H 2 C 1 - C H 2 C 1 v e r s e t z t . Z u r V e r v o l l s t ä n d i g u n g d e r s o f o r t e i n s e t -z e n d e n C H s C l - A b s p a l t u n g w u r d e a n s c h l i e ß e n d 1 h z u m S i e d e n e r h i t z t , w o b e i 2 , 3 g (45,5 m m o l ) ( 9 1 % ) CH3CI i n e i n e r a u f — 7 8 °C g e k ü h l t e n F a l l e k o n d e n -s i e r t e n . A u s d e r L ö s u n g k r i s t a l l i s i e r t e n i m K ü h l -s c h r a n k 1 5 , 8 g ( 8 6 , 4 % ) 3 i n F o r m f a r b l o s e r , a n a l y -s e n r e i n e r K r i s t a l l e . A n a l y s e n a c h s t e h e n d .

1:1-Addukt 7 aus Tetrachloro-N-methylamino-oxalato-0.0'-antimon(V) und Antimon(V )-chlor id-18,4 g (50,0 m m o l ) f e i n g e p u l v e r t e s 3 w u r d e n i n 5 0 m l CH2CI-CH2CI s u s p e n d i e r t u n d u n t e r R ü h r e n b e i 0 °C m i t e i n e r L ö s u n g v o n 1 4 , 9 5 g (50,0 m m o l ) S b C l s i n 20 m l C H 2 C 1 - C H 2 C 1 v e r s e t z t . W ä h r e n d d e r Z u g a b e v e r s c h w i n d e t d i e g e l b e F a r b e d e s S b C l s . N a c h A n w ä r m e n a u f R a u m t e m p . w u r d e d e r F e s t -k ö r p e r a b f i l t r i e r t , m i t CH2CI-CH2CI g e w a s c h e n u n d i . V a k . g e t r o c k n e t . A u s b e u t e 2 6 , 4 g ( 7 8 , 5 % ) f a r b -loses , f e i n k r i s t a l l i n e s 7. A n a l y s e n a c h s t e h e n d .

IR: 3 3 0 5 m , 2 9 5 0 ss, 2 9 2 0 ss, 1698 s s t 1 6 3 5 sst , 1 5 2 0 s m , 1 4 4 2 ss, 1 4 1 5 m , 1 3 8 6 s t , 1 2 6 0 s t , 1 2 2 8 ss,

1 1 5 2 m , 1 0 1 9 s, 895 s, 7 9 6 m , 5 9 6 s, 540 ss, 5 1 3 s, 4 2 0 s m , 384 s t , 3 7 4 sst , 328 S c h , 305 ss, 3 6 1 m s t , 342 s m .

Li-Oxalsäuremethylesler-N-methylimid (9): 5,86 g (50,0 m m o l ) f e i n g e p u l v e r t e s 2 w u r d e n i n 2 5 0 m l E t h e r s u s p e n d i e r t u n d be i 0 °C m i t 5 1 , 0 m m o l e i n e r L i - b u t y l l ö s u n g v e r s e t z t . S o f o r t s e t z t B u t a n e n t -w i c k l u n g e in , d i e d u r c h a n s c h l i e ß e n d e s R ü h r e n be i R a u m t e m p . (6 h ) v e r v o l l s t ä n d i g t w u r d e . D e r f a r b -lose , m i k r o k r i s t a l l i n e u n d e x t r e m f e u c h t i g k e i t s e m p -f i n d l i c h e F e s t k ö r p e r w u r d e a b f i l t r i e r t , m i t E t h e r g e w a s c h e n u n d i . V a k . g e t r o c k n e t . 5 . 7 1 g ( 9 2 , 6 % ) 9. A n a l y s e n a c h s t e h e n d .

IR: 2960 s m , 2 9 3 5 S c h , 2 8 7 0 s, 1 7 2 5 m s t , 1 6 3 1 sst , 1 4 4 1 s, 1 4 1 0 S c h , 1 3 9 5 m , 1 3 7 8 m , 1 2 5 0 s t , 1 1 8 5 S c h , 1 1 5 1 m , 1042 s m , 9 7 9 s, 887 s, 821 ss, 793 m , 7 1 9 s, 5 8 2 s m , 524 s m , 4 5 0 m (sehr b r e i t ) .

Oktachloro - N - methylamidooxalato - 0.0' - 0,N - di -antimon(V) (10): 6 , 5 1 g (52,9 m m o l ) 9 s u s p e n d i e r t i n 1 5 0 m l C H 2 C 1 2 w u r d e n be i — 7 8 °C u n t e r R ü h r e n m i t e i n e r L ö s u n g v o n 44,8 g ( 0 , 1 5 m o l ) S b C l s i n 5 0 m l CH2CI2 t r o p f e n w e i s e v e r s e t z t u n d a n s c h l i e -ß e n d 7 2 h bei d i e s e r T e m p , g e r ü h r t . N a c h A n w ä r -m e n a u f R a u m t e m p . w i r d v o m a u s g e f a l l e n e n L i S b C l ö a b f i l t r i e r t u n d d i e b r a u n e L ö s u n g i . V a k . a u f 5 0 m l e i n g e e n g t . I m T i e f k ü h l s c h r a n k ( — 2 5 °C) f ä l l t a u s d i e s e r L ö s u n g e i n b r ä u n l i c h e r F e s t s t o f f , a u s d e m d u r c h z w e i m a l i g e s U m k r i s t a l l i s i e r e n a u s CH2CI2 1 ,9 g ( 5 , 7 % ) f a r b l o s e s , f e i n k r i s t a l l i n e s 10 e r h a l t e n w u r d e . A n a l y s e n a c h s t e h e n d .

IR: 2920 ss, 1 6 6 5 st , 1 6 3 1 ss t , 1 4 5 3 ss, 1 4 0 5 m , 1 3 4 2 m s t , 1 4 3 4 s m , 1 1 7 0 s, 1020 s m , 8 2 1 m , 5 3 5 s, 508 s m , 470 m , 2 7 7 s m , 3 8 5 S c h , 3 7 9 s t , 3 3 5 s m , 303 ss, 362 m s t .

Oxalsäuremethylesterdimethylamid (4) w u r d e a n a -l o g [13] d a r g e s t e l l t .

IR: 3 0 1 0 ss, 2 9 5 5 s m , 2940 S c h , 2890 S c h , 2 8 7 0 S c h , 2855 S c h , 2 8 1 5 ss, 1 7 4 6 sst , 1 6 6 5 sst , 1 4 5 3 s m , 1 4 3 5 s m , 1 4 1 6 m s t , 1408 m s t , 1 5 0 9 s m , 1 2 8 1 m s t , 1248 s t , 1 1 8 9 ss, 1 0 6 2 s - s s , 1 1 2 2 s t - s s t , 946 s, 980 m , 8 1 9 s m , 7 7 1 s, 740 s - s s , 660 s - s s , 4 3 2 ss, 3 7 0 ss, 348 m . 1:1-Addukt 5 aus 4 und Antimon(V)-chlorid: Zu 6,56 g (50,0 m m o l ) 4 i n 30 m l CH2CI2 w i r d be i — 7 8 °C u n t e r R ü h r e n e i n e L ö s u n g v o n 1 4 , 9 5 g (50,0 m m o l ) A n t i m o n ( V ) - c h l o r i d i n 20 m l C H 2 C 1 2

g e t r o p f t . D i e R e a k t i o n s l ö s u n g w i r d a n s c h l i e ß e n d b e i — 4 0 °C i . V a k . v o l l s t ä n d i g e i n g e e n g t . 5 f ä l l t d a -b e i i n f a r b l o s e r , f e i n k r i s t a l l i n e r u n d s e h r f e u c h t i g -k e i t s e m p f i n d l i c h e r F o r m a n . A u s b e u t e q u a n t i t a t i v . A n a l y s e n a c h s t e h e n d .

IR: 3055 ss, 3 0 1 0 ss, 2 9 5 5 s, 1 7 5 2 ss t , 1 6 3 2 st , 1 4 6 3 S c h , 1 4 1 9 m s t , 1400 s t , 1 3 7 8 S c h , 1 4 4 7 s t , 1 2 6 5 s t , 1 2 2 6 s, 1 1 9 0 ss, 1048 ss, 1 1 4 9 m s t , 986 s m , 903 m , 8 1 9 m , 7 9 3 s, 7 1 1 m , 620 s m , 467 ss, 3 7 0 S c h , 3 5 5 sst , 330 S c h .

Tetrachloro -N.N- dimethylaminooxalato - 0.0' - anti -mon(V) (6):

a) T h e r m i s c h e Z e r s e t z u n g d e s 1 : 1 - A d d u k t e s 5 a u s 4 u n d A n t i m o n ( V ) - c h l o r i d .

8,6 g (20,0 m m o l ) 5 w e r d e n i . V a k . 4 h a u f 7 0 °C


e r w ä r m t . U n t e r C H 3 C 1 - A b s p a l t u n g b i l d e t s ich 6, d a s n a c h e i n m a l i g e m U m k r i s t a l l i s i e r e n a u s CH2CI2 r e i n ist . F a r b l o s e , f e i n e K r i s t a l l e . A u s b . 4,8 g ( 6 3 % ) .

b) A u s O x a l s ä u r e m e t h y l e s t e r d i m e t h y l a m i d (4) u n d A n t i m o n ( V ) - c h l o r i d .

6 ,56 g (50,0 m m o l ) 4 i n 5 0 m l 1 . 2 - D i c h l o r e t h a n w e r d e n be i 0 °C m i t 1 4 , 9 5 g (50,0 m m o l ) S b C l 5 v e r -s e t z t . A n s c h l i e ß e n d w i r d 4 h a m R ü c k f l u ß e r h i t z t . I n e i n e r a u f — 7 8 °C g e k ü h l t e n F a l l e w e r d e n 2,2 g ( 8 7 , 1 % ) CH3CI k o n d e n s i e r t . A u s d e r L ö s u n g kri-s t a l l i s i e r e n b e i m A b k ü h l e n 10,7 g ( 5 6 , 5 % ) 6. A n a -l y s e n a c h s t e h e n d .

IR: 2950 ss, 2920 ss, 2 8 5 5 ss, 1 7 4 5 sst , 1 6 6 0 s t - s s t , 1 4 1 0 s, 1398 st , 1250 s, 1 2 1 9 m , 1046 ss, 1 1 4 9 s, 942 s, 830 m , 703 m s t , 5 9 2 ss, 562 ss, 507 s, 432 s, 3 7 5 S c h , 366 st , 330 ss.

1: 1-Addukt 8 aus TetracMoro-N .N-dimethyl-aminooxalato-O.O'-antimon(V) 6 und Antimon(V)-chlorid:

a) A u s O x a l s ä u r e m e t h y l e s t e r d i m e t h y l a m i d 4 u n d A n t i m o n ( V ) - c h l o r i d . Z u 6 ,56 g (50,0 m m o l ) 4 in 30 m l CH2CI2 w e r d e n be i — 7 8 °C 29,9 g (0,1 m o l ) S b C l s i n 40 m l CH2CI2 g e t r o p f t . D i e f a r b l o s e R e a k -t i o n s l ö s u n g w i r d b e i — 4 0 °C z u m T r o c k n e n einge-e n g t , w o b e i b e r e i t s CH3CI a b s p a l t e t . A n s c h l i e ß e n d

w i r d be i R a u m t e m p . i . V a k . r e s t l i c h e s C H 3 C 1 e l imi-n i e r t , w a s n a c h ca. 5 h b e e n d e t i s t . N a c h U m k r i -s t a l l i s i e r e n a u s CH2CI2 w e r d e n 24,3 g ( 7 1 . 6 % ) f a r b -loses, f e i n k r i s t a l l i n e s u n d f e u c h t i g k e i t s e m p f i n d l i -c h e s 8 e r h a l t e n .

b) A u s T e t r a c h l o r o - N . N - d i m e t h y l a m i n o o x a l a t o -O . O ' - a n t i m o n ( V ) (6) u n d A n t i m o n ( V ) - c h l o r i d .

18,98 g (50,0 m m o l ) 6 w e r d e n i n 50 m l C H 2 C 1 2

g e l ö s t u n d bei 0 °C m i t e i n e r L ö s u n g v o n 1 4 , 9 5 g (50,0 m m o l ) S b C l s i n 20 m l C H 2 C 1 2 v e r s e t z t . A u s d e r R e a k t i o n s l ö s u n g k r i s t a l l i s i e r e n i m T i e f k ü h l -s c h r a n k ( — 2 0 °C) 2 1 , 6 g ( 6 3 , 7 % ) 8. A n a l y s e n a c h -s t e h e n d .

IR: 1 6 3 5 sst , 1 6 6 2 sst , 1 4 2 5 S c h , 1420 m s t , 1408 st , 1 3 5 1 s , 1 2 2 3 s m , 1050 s, 1 1 6 8 ss, 950 ss, 840 s m , 801 ss, 703 m , 604 s, 5 5 8 s, 5 2 9 s m , 4 1 8 s, 396 S c h , 380 S c h , 2 6 9 sst , 3 6 5 S c h , 346 S c h .

D e m I n s t i t u t f ü r A n o r g a n i s c h e C h e m i e d e r U n i -v e r s i t ä t S t u t t g a r t d a n k e n w i r f ü r d i e B e r e i t s t e l l u n g v o n G e r ä t e n u n d C h e m i k a l i e n . D e r D e u t s c h e n F o r -s c h u n g s g e m e i n s c h a f t u n d d e m F o n d s d e r C h e m i -s c h e n I n d u s t r i e s i n d w i r f ü r f i n a n z i e l l e H i l f e z u D a n k v e r p f l i c h t e t .

Tab. VI. Analysenergebnisse der Verbindungen 1-10. Substanz (Molmasse) C H N Cl Sb Schmp. [°C] C4H7N03 (2) Ber. 41,03 6,03 11,96 — — 83 (117,10) Gef. 40,97 6,15 11,90 — — (Lit. [12] 84) C4H6DN03 (2, ND statt NH) Ber. 40,68 6,82* 11,86 — — 81 (118,10) Gef. 40,52 ? 11,79 — —

C2Cl804Sb2 (1) Ber. 3,91 — — 46,11 39,58 158 (615,10) Gef. 4,04 — — 45,85 39,23 (Lit. [5] 159) C3H4NCl403Sb (3) Ber. 9,86 1,10 3,83 38,79 33,30 216 (365,60) Gef. 9,74 1,27 3,82 38,35 33,40 C3H3DNCl403Sb (3, ND statt NH) Ber. 9,83 1,73* 3,82 38,68 33,21 202 (366,6) Gef. 9,84 1,09 3,82 38,53 33,40 C3H4NCl903Sb2 (7) Ber. 5,36 0,69 2,08 47,45 36,21 170 (Zers.) (672,50) Gef. 5,40 0,81 2,10 47,54 36,12 C4H6NLi03 (9) Ber. 39,05 4,92 11,38 — — ab 120 Zers. (123,10) Gef. 37,42** 5,04 11,12 — —

C3H3NCl803Sb2 (10) Ber. 5,74 0,48 2,23 45,15 38,76 260 (Zers.) (628,20) Gef. 5,78 0,48 2,26 44,81 38,51 C5H9NO3 (4) Ber. 45,79 6,93 10,68 — —

(131,23) Gef. 45,57 6,88 10,72 — —

C5H9NCl503Sb (5) Ber. 13,96 2,11 3,26 41,21 28,30 75 (Zers.) (430,10) Gef. 14,04 2,15 3,28 40,91 28,20 C4H6NCl403Sb (6) Ber. 12,66 1,60 3,69 37,35 32,06 128-129 (379,61) Gef. 12,29 1,52 3,53 37,11 31,78 C4H6NCl903Sb2 (8) Ber. 7,08 0,89 2,06 47,02 35,87 136-138 (Zers. (678,56) Gef. 6,96 1,10 1,99 46,79 35,90 * Mit dem zur Verfügung stehenden CHN-Analyser Mod. 240 (Perkin Eimer) kann nur H oder D bestimmt werden. ** Wird wegen gleichzeitiger Anwesenheit von Li und Bildung von Li2CÖ3 trotz Zugabe von WO3 zu niedrig.

[1] M. Rössler, Teil einer der Universität Stuttgart einzureichenden Dissertation.

[2] R. A. Laber und A. Schmidt, Z. Anorg. Allg. Chem. 428, 209 (1977).

[3] P. Pfeiffer, Liebigs Ann. Chem. 376, 285 (1910). [4] A. Rosenheim und W. Loewenstamm, Ber. Dtsch.

Chem. Ges. 35, 1116 (1902).

[5] R. A. Laber und A. Schmidt, Chem. Ber. 108, 1125 (1975).

[6] R. A. Laber und A. Schmidt, Z. Anorg. Allg. Chem. 416, 32 (1975).

[7] International Tables for X-Ray Crystallography, Kynoch Press, Birmingham 1974.

[8] XTL/E-XTL, Programmsystem zur Bestim-


mung von Kristallstrukturen, Syntex Analytical Instruments Inc., Cupertino, Kalifornien, USA 1976.

[9] D. T. Cromer und J. T. Waber, in: International Tables for X-Ray Crvstallography, Vol. IV., S. 771 ff., The Kynoch Press, Birmingham 1974.

[10] C. K. Johnson, ORTEP Report ORNL-3794, Oak Ridge National Laboratory, Tennessee, USA 1965.

[11] B. Kruss und M. L. Ziegler, Z. Anorg. Allg. Chem. 401, 89 (1973).

[12] L. Brun und C. I. Bränden, Acta Crystallogr. 20, 749 (1966).

[13] P. P. T. Sah und S. L. Chien, J. Am. Chem. Soc. 53, 3901 (1931).

[14] R. Paul und S. Tchelitcheff, Bull. Soc. Chim. Fr. 1960, 150.

Reaktionsprodukte yon Oxylsäuremethylester-N-methylamiden...

Documents

Transcript of Reaktionsprodukte yon Oxylsäuremethylester-N-methylamiden...