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304 R. K. MEHTA AND V. C. SINGHI

Cyclopentadienyl-tris( trifluorphosphin) -mangan

In eine Bestrahlungsapparatur der Firma 0 . Fritz GmbH, Normschliff-Aufbaugeräte, werden 2,0 g (9,8 mMol) CpMn(CO)3, gelöst in 340 ml THF, gegeben. Bei 0 °C wird mit einem Quecksilberhochdruckbrenner TQ 150 der Quarzlampen GmbH, Hanau, bestrahlt, wo-bei sich die roten THF-Komplexe bilden. Danach läßt man PF3 durch die Lösung perlen, bis sie sich nach gelb verfärbt hat. Dann bestrahlt man wieder bei 0 °C und setzt bei 5 °C mit PF3 um. Nach der dritten Be-strahlung muß die Temperatur bei der Einwirkung von PF3 auf 20 °C erhöht werden. Dieses Verfahren wie-derholt man sechsmal, wobei die Bestrahlungszeit je-weils 8 Stdn. beträgt.

Nach dem Abziehen des Lösungsmittels wird der schmutziggelbe Rüdestand in Äther aufgenommen und filtriert. Nach dreimaliger Wiederholung dieser Proze-

1 2 9 . M i t t . : T H . K R Ü C K , G . SYLVESTER U. I . P . K U N A U , A n -gew. Chem. 83, 725 [ 1 9 7 1 ] ; Angew. Chem. internat. Edit. 10, 725 [1971] .

2 T H . K R Ü C K U. L . K N O L L , u n v e r ö f f e n t l i c h t e E r g e b n i s s e . 3 TH. KRÜCK, Z. Naturforsch. 19 b , 165 [1964] . 4 T H . K R Ü C K , W . HIEBER U. W . L A N G , A n g e w . C h e m . 7 8 ,

208 [1966] ; Angew. Chem. internat. Edit. 5, 247 [1966 ] . 5 T H . K R Ü C K U. L . K N O L L , i n V o r b e r e i t u n g . 6 TH. KRÜCK U. A. PRASCH, Z. anorg. allgem. Chem. 356,

1 1 8 [ 1 9 6 8 ] . 7 M . HERBERHOLD U. C . R . JABLONSKI, C h e m . B e r . 1 0 2 , 7 6 7

[1969] .

dur wird bei 40 °C/10 3 Torr sublimiert. Man erhält gelbe Kristalle von unangenehmem Geruch. Ausbeute: 2,6 g = 70% d. Theorie. Schmp.: 1 6 5 - 1 6 7 ° C .

A n a l y s e : H C F P M n

B e r . : 1,31 15,64 44,54 24,21 14 ,13° 0

G e f . : 1,6 16,5 44,5 23,9 14,2 %

M G W (massenspektr.) : 384.

Unser besonderer Dank gilt dem Ministerium für Wissenschaft und Forschung des Landes NRW, das diese Arbeit finanziell unterstützte, und der Badischen Anilin- & Sodafabrik AG, Ludwigshafen, für die Aus-führung der Elementaranalyse.

8 W . STROHMEIER U. F . J . MÜLLER, C h e m . B e r . 1 0 0 , 2 8 1 2 [ 1967 ] .

9 J . MÜLLER, K . FENDERL U. B . MERTSCHEK, C h e m . B e r . 1 0 4 , 700 [1971] .

1 0 T . S . PIPER, F . A . C O T T O N U. G . WILKINSON, J . i n o r g . nuclear Chem. 1 , 1 6 5 [1955] .

11 Für die Aufnahme der Massenspektren danken wir Herrn D i p l . C h e m . H . V I L T E R .

12 Für die Aufnahme der NMR-Spektren danken wir Herrn D r . P . JUNKES.

Metal Complexes of N-hydroxyethylnaphthalideneimine Schiff Base

R . K . M E H T A a n d V . C . SINGHI Department of Chemistry, University of Jodhpur, Jodhpur (India)

(Z. Naturforsch. 27 b, received September 14, 1971, revised October 2, 1971)

The S c h i f f base, A^-hydroxyethylnaphthalideneimine forms solid complexes with Mn (II ) , Co ( I I ) , N i ( I I ) , Cu (II ) , Z n ( I I ) , C d ( I I ) , P d ( I I ) and U 0 2 ( I I ) . The structures of these compounds have been discussed on the basis of their elemental analysis, magnetic moment values and electro-nic spectral data. These studies have conclusively proved that U 0 2 ( I I ) and Mn( I I ) complexes are octahedral in shape whereas the Cu( I I ) complex molecule displays a square planar or tetra-gonally distorted octahedral configuration. Co ( I I ) , Ni ( I I ) , Zn (II) and Cd (II) complexes are tetra-hedral in structures while the Pd (II) compound is square planar.

Although Amaryl and A^-alkyl salicylideneimines S c h i f f bases and their metal complexes have been intensively studied 1 , those of the ligands in which the amino groups are attached to hydroxyalkyl groups have received little attention 2 ' 3 . It is, there-fore, considered interesting to study, the metal com-plexes of the S c h i f f base derived f rom 2-hydroxy-1-napthaldehyde and ethanolamine. The present

Requests for reprints should be sent to Dr. R. K. MEHTA, Lecturer in Inorganic Chemistry, Department of Chemistry, Univ. of Jodhpur, Jodhpur (Indien).

paper describes the results of the investigation on the complexes of M n ( I I ) , C o ( I I ) , N i ( I I ) , C u ( I I ) , Z n ( I I ) , C d ( I I ) , P d ( I I ) and U 0 2 ( I I ) with N-hy-droxyethylnaphthalideneimine S c h i f f base and these are represented by the Structures I and II.

Experimental

Materials: 7V-hydroxyethylnaphthalideneimine was prepared by boiling a mixture of equimolecular propor-tions of 2-hydroxy-l-naphthaldehyde and ethanolamine in dry benzene over a waterbath under reflux for two

METAL COMPLEXES OF A-HYDROXYETHYLNAPHTHALIDENEIMINE 305

hours. Afterwards, excess of benzene was distilled off and the solid residue was extracted into methanol. The clear solution was filtered, concentrated and cooled when yellow crystals of S c h i f f base were obtained. These were filtered out and recrystallised from metha-nol, m.p. 145 °C. Found: C 72.41, H 6.02, N 6.49, [C1 0H6 (OH)CH = N(CH 2 ) 2 OH] requires C 72.55, H 6.05, and N 6.51%.

The complexes of Mn(II ) , Co (II) , Ni ( I I ) , Cu(II ) , Zn(II ) , Cd (II) , Pd ( I I ) , and U0 2 ( I I ) with iV-hydroxy-ethylnaphthalideneimine were prepared by the method o f Y A M A D A e t a l . 4 .

All these compounds are found to be insoluble in water but partially soluble in alcohol, pyridine and other organic solvents.

Measurements: The combustion analysis was con-ducted by using Hosli's electrical micro combustion furnace. Gallenkamp Semi-micro ebulliometer was employed for molecular weight determinations using ethanol as the solvent. The magnetic measurements were made on Gouy apparatus. Diamagnetic correc-tions were applied and finally the molar susceptibility and magnetic moment were evaluated at 303 °K. The electronic absorption spectra of the complexes in solu-tion were determined with a VEB Carl Zeiss Jena, VSU-2P spectrophotometer at room temperature.

Colour, molecular weight and elemental analyses data of these compounds are given in Table 1 and the magnetic data in Table 2.

Results and Discussion

Manganese(II) Complex: It corresponds to the composition [MnL 2 ] where LH = [ C 1 0 H 6 ( O H ) C H = N (CH 2 ) 2 O H ] and its magnetic moment is found

to be 5.83 B.M. at room temperature (30 ° C ) . The magnetic moments of both octahedral or tetrahedral M n ( I I ) compounds should be nearly 5 .92 B.M. since a 6S ground state persists in all symmetries of M n ( I I ) complexes 5 . The little lower value of the magnetic moment of this compound may be due to spin exchange in its solid state or to the presence of little M n ( I I ) species which may be caused due to aerial oxidation as reported earlier 1 f or such com-plexes.

In order to decide whether hexacoordination is due to intermolecular association or to intramolecu-lar combination of — OH group with the central M n ( I I ) , the knowledge pertaining to its molecular weight is quite helpful. The molecular weight of the M n ( I I ) complex under investigation is found to be 475 wrhich excludes the probability of intermolecu-lar association and it is most likely that the intra-molecular M — OH bond may be present in the com-pound. This situation is best represented by an octa-

hedral structure f o r the M n ( I I ) complex which seems to have been favoured by steric condition.

Thus based on elemental analysis, molecular weight and magnetic results an octahedral structure is assigned to this complex in which the third co-ordination position of the M n ( I I ) is occupied by the — OH group and the S c h i f f base functions as a tridentate ligand (Fig. 1 ) .

WHERE M=Co(n), Ni(IT), Cu (H), Z n ( n ) . C d ( n ) , Pd(II) AND U02(H)

WHERE M =Mn (H)

Cobalt(II) Complex: The data summarized in Table 1, give the composition [CoL 2 ] f or this com-pound in which LH = [C 1 0 H 6 (OH)CH = N(CH 2 ) 2 OH] and thus indicate 1 : 2 metal-ligand stoichiometry in it. The magnetic moment of this compound at room temperature (30 °C ) is found to be 4.61 B.M. The electronic absorption spectra of this complex in dioxane and pyridine consist of only one absorption band with its peak at 13,700 c m - 1 . The band may be assigned to the transition 4 T j 4 A 2 which may be due to the tetrahedral configuration of the com-plex. Thus based on molecular weight spectral and magnetic data a high-spin tetrahedral structure (I ) is assigned to the Co (II) complex under study, in wrhich the S c h i f f base functions as a bidentate ligand.

Ni(II) Complex: The greenish yellow N i ( I I ) complex displaying a metal-ligand ratio of 1 : 2 , can be represented by the formula [NiL.,] , where L H = [ C 1 0 H 6 ( O H ) C H = N ( C H 2 ) o O H ] . The magne-tic moment of this compound at room temperature ( 3 0 ° C ) is found to be 3.82 B.M. In a four co-valent, paramagnetic, high-spin, tetrahedral Ni ( II ) complex the ground term is 3TX and the moments lie

306 R. K. MEHTA AND V. C. SINGHI

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between 3.2 and 4 .0 B.M. at room temperature. Based on this the Ni ( I I ) compound under study should display tetrahedral configuration (I) in which the ligand acts as a bidentate one.

Copper(II) Complex: The molecular weight and the elemental analyses (Table 1) of the olive-green c o p p e r ( I I ) compound suggest 1 : 2 metal-ligand stoichiometry. Its composition may therefore be given by [CuL 2 ] where LH = [C 1 0 H 6 (OH) CH = N ( C H 2 ) 2 O H ] . The molecular weight results clearly indicate its existence as a monomer in the solid state. The copper ( I I ) complex under study exhibits a magnetic moment of 1.87 B.M. at room tempera-ture (30 ° C ) . The magnetic-moment of planar-com-plexes are generally lower (1.8 — 1.9 B.M.) than those of octahedral complexes (//eff 1.9 — 2.0 B . M . ) . As planar stereochemistry may be considered as the limiting case of a tetragonally distorted octa-hedral stereochemistry, the separation of the inter-action terms ( i . e . between ground term 2 B] ? and the components of 2To<r term) is large in square-planar complexes than in octahedral complexes which possibly explains the lower magnetic mo-ments of square-planar complexes 5 ' 6 . The magnetic moments of perfect tetrahedral complexes are higher than square planar or octahedral complexes due to spin-orbit coupling and are temperature dependent. The electronic absorption spectra in methanol of the C o p p e r ( I I ) compound consists of a broad band at about 1 6 7 5 0 c m - 1 and second band at 24210 c m - 1 . The appearance of an absorption band at 16750 c m - 1 and the magnetic moment value of 1.87 B.M.. support a square planar or tetragonally distorted octahedral configuration of the c o m p l e x 7 ' 8 . The band exhibit bathochromic shift in pyridine which may be attributed to the association of two pyridine molecules to the C u ( I I ) ion thus forming an octa-hedral complex. The S c h i f f base appears to ex-hibit bidentate function in this case.

Zinc(Il), Cadmium(ll), Uranyl(II) and Palla-dium (II) Complexes

These compounds were found diamagnetic, as ex-pected and possess 1 : 2 metal-ligand stoichiometry as supported by their elemental analysis and mole-cular weight data. Thus their composition may be expressed by [ { C 1 0 H 6 ( O ) C H = N(CH 2 ) 2 OH} 2 M(II ) l , where M stands for Z n ( I I ) , C d ( I I ) , U 0 2 ( H ) and P d ( I I ) . Consequently Z n ( I I ) and Cd (II ) com-

METAL COMPLEXES OF A-HYDROXYETHYLNAPHTHALIDENEIMINE 3 0 7

Formulae Mass Sus- Mo lar Sus- Magnet i c N o . o f Poss ib le cept ib i l i ty cept ib i l i ty M o m e n t s unpaired b o n d t y p e 7 s x 106 Xm X 106 [left in B . M . electrons

[ { C I 0 H 6 ( O ) C H = [ { C I 0 H 6 ( O ) C H = [ { C 1 0 H 6 ( O ) C H = [ { C I 0 H 6 ( O ) C H = [ { C 1 0 H 6 ( O ) C H = [ { C I 0 H 6 ( O ) C H = [ { C I 0 H 6 ( O ) C H = [ { C I 0 H 6 ( O ) C H =

= N ( C H 2 ) 2 O H } 2 M n ] = N ( O H 2 ) 2 O H } 2 C O ] = N ( C H 2 ) 2 O H } 2 N i ] = N ( C H 2 ) 2 0 H } 2 C U ] = N ( C H 2 ) 2 O H } 2 Z n ] = N ( C H 2 ) 2 O H } 2 C d ] = N ( C H 2 ) 2 0 H } 2 P d ] = N ( C H 2 ) 2 O H } 2 U O o ]

28 .2767 17.3498 11.7577

2.4057

13658.34 8447 .60 5722.54 1182 4 2

5.83 4.61 3.82 1.87 d iamagnet i c d iamagnet i c d iamagnet i c d iamagnet i c

s p 3 d 2

sp 3

sp 3

sp 3

Table 2. Magnetic data of the complexes of iV-hydroxyethylnaphthalideneimine S c h i f f base at 303 ° K .

pounds possess tetrahedral configuration in which the S c h i f f base functions as a bidentate ligand. U 0 2 ( I I ) complex, probably possesses an octahedral structure as is usually displayed by U 0 2 ( I I ) 9 . In this complex the S c h i f f base acts as a bidentate ligand. Pd (II) greatly favours a square planar con-figuration. YAMADA et a l . 1 0 have suggested square planar structure for a number of iV-alkylsalicyl-ideneiminato P d ( I I ) complexes. A similar structure is suggested for the P d ( I I ) complex under investi-gation, in which the S c h i f f base functions as a bidentate ligand. The solution spectra of P d ( I I )

1 R . H . HOLM, G . W . EVERETTE, JR., a n d A . CHAKRAVORTY, Prog. Inorg. Chem. 7, 83 [19661-

2 S . YAMADA, S . KUGE, a n d K . YAMANOUCHI , B u l l . C h e m . Soc. Japan 40, 1864 [1967] .

3 S . N . PODDAR, K . D A Y , J . HALDAR, a n d NATHSARKAR, J. Indian Chem. Soc. 47, 743 [1970 ] .

4 S . YAMADA. H . NISHIKAWA, a n d E . YOSHIDA, B u l l . C h e m . Soc. Japan 39, 994 [1966] .

5 B . N . FIGGIS a n d C . M . HARRIS. J . c h e m . S o c . [ L o n d o n ] 1959, 855.

complex in methanol and pyridine showed negli-gible difference which indicates that the pyridine molecules do not coordinate to the central P d ( I I ) ion and these results agree with those of YAMADA et a l . 1 0 .

The configurations reported in this communica-tion are in agreement with those of V-hydroxy-ethylsalicylideneimine complexes 3 w7ith wrhich it is structurally similar.

The authors are thankful to University Grants Com-mission New Delhi (India) for the award of a fellow-ship to one of them (V.C.S.).

8 B. N. FIGGIS and J. LEWIS, Prog. Inorg. Chem. 6, 37 [1964 ] .

7 L . SACCONI a n d M . CIAMPOLINI, J . c h e m . S o c . [ L o n d o n ] 1 9 6 4 , 276.

8 L. SACCONI et al., J. Inorg. Nucl. Chem. 19, 73 [ 1 9 6 1 ] . 9 J. SELBIN, Angew. Chem. internat. edn. 5, 712 [1966 ] ,

10 S. YAMADA, Coordin. Chem. Rev. 1, 415 [1966 ] .