NOTES

(Chloro) bis ('YJ5-fluorenyl)-N - aryldithiocarbamatotita-nium(IV) Compounds

N. K. KAUSHIK*: ANAND K. SHARMA& G. S. SoDHIDepartment of Chemistry, University of Delhi, Delhi 110007

Received 4 December 1980; revised and accepted 20 January1981

Some (chloro)bis('l5-fluorenyl)- N - aryldlthiocarbamatotita-nium(IV) compounds of the type (115-C13H.).Ti(S.CNHR)Clwbere R = different aryl groups have been prepared by thereaction of (dichloro)bis('l5-fluorenyI)titanium(IV) with ammo-nium N-aryldithiocarbamates. Probable structures of thesederivatives have been assigned on the basis of molecular weight,conductance, infrared spectral and magnetic susceptibility studies.

DITHIOCARBAMATES, by virtue of their lowcharge and small bites (2.8-2.9 A), are well

suited for stabilisation of higher coordination numbersof metals. For instance, eight-coordination occursin Ti (SzCNR2)4 and six-coordination in ClzTi(S2CNR2)2 (ref. 1). Penta-coordinated derivatives havealso been reported 2-4. The present note deals with pre-paration and characterisation of the complexes of thetype ('YJ5_C13H9hTi (S2CNHR)CI where R = phenyl,0-, m-,p-tolyl, 0-, m-,p-chlorophenyl,p-bromophenyl,p-iodophenyl and p-methoxyphenyl groups. In allthese complexes the dithiocarbamate groups arebidentate, similar to the dithiocarbamates reportedearlier>".

All the reactions were carried out in strictly anhy-drous medium using interchangeable glass-joints.Ammonium dithiocarbamates, NHiS2CNHR), pre-pared by the method described by Klopping andKerk", were dried in vacuo over P20/i' (Dichloro) bis('YJ5fluorenyl)titanium(IV)was prepared by the reac-tion of titanium(IV) tetrachloride with sodium

salt of fluorene in dimethoxyethane with continuousstirring for 18-20 hr under dry nitrogen". Nitro-benzene was purified for conductance measurementsby the method described by Far et al. lOTitanium,sulphur, nitrogen and chlorine were estimated bystandard methods-'.

Molecular weights were determined by the ebullio-metric method in benzene. Conductance meaure-ments were carried out in nitrobenzene on a Beck-mann conductivity bridge (model RC-18A). Table 1lists analytical and physical data of the complexes.

IR spectra were recorded in KBr medium, in therange 4000-200 crrr? on a Perkin-Elmer-621 infra-cord spectrophotometer. Electronic spectra of thecomplexes were run on a Perkin Elmer 4000Ainstrument in the range 400-750 nm. Magneticmeasurements were made by Gouy's method usingCuS04.5HIP as the cali brant.

All the complexes were prepared in a similarmanner. (Dichloro) bis ('YJ5-f1uorenyl)titanium(IV)(2.24 g, 0.005 mol) was stirred in dimethoxyethane(-- 100 ml) with stoichiometric amounts of anhy-drous ammonium salt of dithiocarbamic acid for16-18 hr under dry nitrogen. The solution was thenfiltered and its volume was reduced to -- 20 ml.Crystals of the product were obtained by addingexcess of pet. ether (60-80°C). The excess of solventwas removed in vacuo and the compound dried overP20S (-- 2 hr),

It is evident from the analytical data that onemole of (dichloro) bis('YJs-f1uorenyl)titanium(IV)reacts with one mole of ammonium dithiocarbamatesaccording to the following equation,(.,l-C13H9)2TiC12+ NH4(S2CNHR) --*

('YJ5-ClaH9hTi(S2CNHR)CI+ NH4ClConductance measurements (-- 0.28 ohm-1 em"

mol-1 for 5 x 10-lM solution) show that all the

TABLE1 - ANALYTICALANDPHYSICALDATAOF ('l'-R).Ti(SICNHR)Cl COMPLEXES

Compound" Dec. Found (Calc.) % Mol. w ttemp. Found

°C C H N S Ti CI (Calc.)

(l1'-R).Ti[S.C HC.H,}CI 160--164 68.01 4.21 2.28 10.92 8.16 6.23 580(68.10) (4.13) (2.40) (11.01 ) (8.24) (6.11 ) (581)

('l"-R).Ti[S.CNH(o-CH.C.H.)ICI 106--108 68.50 4.25 2.23 10.71 7.85 6.02 593(68.52) (4.37) (2.35) (10.75) (8.04) (5.96) (595)

('l'-R).Ti[S.CNH(m-CH3C.H.)}CI 105-107 68.42 4.30 2.25 10.60 8.00 6.03 594(68.52) (4.37) (2.35) (10.75) (8.04) (5.96) (595)

('l5-R).Ti[S.CNH(p-CH.CeH.)}CI 140--142 68.43 4.43 2.30 10.58 8.09 5.90 594(68.52) (4.37) (2.35) (10.75) (8.04) (5.96) (595)

('l·-R).Ti[S.CNH(o-CIC.H.)}Cl 100--102 64.21 3.79 2.21 10.28 7.65 11.59 614(64.30) (3.73) (2.27) (10.39) (7.78) (J 1.53) (616)

('l'-RhTi[S.CNH(m-CIC.H.)}CI 90--96 64.32 3.85 2.22 10.31 7.68 11.63 612(64.30) (3.73) (2.27) (10.39) (7.78) (11.53) (616)

('l"-RhTi[S.CNH(p-CIC.HJ}Cl 112-114 64.14 3.86 2.10 10.22 7.59 11.45 614(64.30) (3.73) (2.27) (10.39) (7.78) (11.53) (616)

('l'-R).Ti[S.CNH(p-BrC.H.)}CI 148-157 59.80 3.40 2.19 9.52 7.20 5.24 658(59.97) (3.48) (2.12) (9.69) (7.25) (5.38) (660)

('l'-R).Ti[S2CNH(1'-IC.H.)}CI 146-149 55.84 3.20 2.01 9.01 6.71 5.09 706(55.99) (3.25) (1.98) (9.05) (6.77) (5.02) (707)

('l'-R).Ti[S.CNH(p-OCH.C.H.)]CI 150--154 66.65 4.21 1.68 10.35 7.72 5.68 609(66.73) (4.25) (1.63) (10.47) (7.83) (5.81) (611)

*R = CuH.

847

INDIAN J. CHEM., VOL. 20A, AUGUST 1981

complexes are essentially non-electrolytes in nitro-benzene. From molecular weight measurements it isconcluded that these complexes are monomeric.Magnetic susceptibility values show that the comp-lexes are diamagnetic. The compounds are yellow-ish-brown to brown in colour.

All these complexes are stable solids in inert atmos-phere. They are very sensitive to moisture butrelatively much stable in dry air. The compounds aresoluble in methanol, ethanol and benzene and areinsoluble in chloroform, carbon disulphide, dichloro-methane and acetone.

A coordination number of 5 may be assigned totitanium in these complexes if the dithiocarbamateligand is bidentate and each fluorenyl groupoccupies one coordination site, however the coordi-nation number 4 would result if the dithiocarbamateligand behaves as S-bonded mono dentate ligand.These two possibilities can be distinguished by in-frared spectral studiesl2-l4. Bonati and Ugo12 showedthat if the dithiocarbamate ligand is bidentate, asingle band due to vC-S around 1000 cm-1 is found.In the case of unidentate dithiocarbamates, as inEtS2CNEt2 , a doublet is observed around 1005 and"'" 983 em:", due to two nonequivalent v C-S vibra-tions. All the present complexes show only a singlemedium intensity band around 1000 ern:" (apartfrom C-H deformation band of fluorenyl group).This indicates the presence of four-membered ringsystems in the complexes and supports the bidentatenature of the dithocarbamate ligands. Bands occur-ing around 1500, 995, 380 and 360 cm-1 in thesecompounds have been assigned to v(C.:.:..:N),v(C :..:.:S), v(Ti - Cl) and v(Ti-S) vibrations res-pectively. The bands occurring at •.....3100, •.....1440,"'" 1020 and "",815 crrr? in all these compounds showthe presence of 7t-bonded fluorenyl groups. Fromabove discussion it is evident that if the fluorenylgroups are assumed to occupy single coordinationsites, then infrared spectral data favour a penta-

. coordinated structure for all these complexes.The electronic spectra of all these complexes re-

corded in nujol, exhibit a single band in the region of24980-24300 cm ". This band may be assigned tocharge transfer-", which is in accord with electronicconfiguration (n -1) d", nSo of titanium in all thesecomplexes.

References1. BHAT, A. N., FAY, R. C., LEWIS,D. F., LINDMARK,A. F.

& STRAUSS,S. H., Inorg. Chem., 13 (1974), 886.2. KAUSHIK, N. K., BHUSHAN, B. & CHHATWAL, G. R.,

Transition met. Chem., 3 (1978), 215.3. KAUSHIK, N. K., BHUSHAN, B. & CHHATWAL,G. R.,

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Z. Naturforsch.., 34b (1979), 949.5. COUTTS, R. S. P. & WAILES, P. C., Aust. J. Chern., 27

(1974), 2483.6. CoUTTS, R. S. P. & WAILFS,P. C., J. organometal, Chern.,

. 84 (1975), 47.7. CoUTTS, R. S. P., WAILES, P. C. & KINGSTON,J. V., Aust.

J. Chem., ·23 (1970), 463. . .8. KLijpPING, H. L. &.VANDERKERK,.G. J.. M., Rec. Trav,

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11. VOGEL,A. I., A text-book of quantitative inorganic analysis(Longmans, Green, London), 1964,256, 460, 466,544.

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13. BRADLEY,D. C. & GITLITZ, M. H., J. chern. Soc. (A),(1969), 1169.

14. DOMENTCANO,A., VOCTAGO,A., ZAMBONELLI,L., LoADER,P. L. & VENANZI,L. M., Chern. Commun., (J968), 476.

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Metallic Complexes as Ligands: Part IIt-Nickcl(II)Complex of the Schiff Base Derived from 3-Formyl-salicylic Acid & Ethylenediamine as Ligand for

Ti, Zr,Sn,P&B

K. DEY*, A. K. BISWAS& A. K. SINHA RoyDepartment of Chemistry, University of Kalyani,

Kalyani 741 235

Received 22 September 1980; revised and accepted5 December 1980

Ni(II) .complex of quadridentate schiff base obtained by thecondensation of 3-formylsalicylic acid with ethylenediamine(=3-fsaen-H.) has been employed as a ligand to synthesise avariety of complexes (bimetallic type). For example, 3-fsaen-(H2)M has been successfully silylated and lithiated to get3-fsaen (SiMe3)2M and 3-fsaen(Li)2M, which, in turn, reactwith R.MX2(R = CH., C.H., ",-C,H.; M = .Sn, Ti; X=CI),R2BCl(R=C.H.), RPCI2 (R = CH3, C.H.) and O=PCI.to yield complexes of the type 3-fsaen MM'R., 3-fsaen M(BR.).3-fsaen M(PR) and 3-fsaen MP(CI)=O. These complexeshave been characterized with the help of elemental analyses,molecular weights, and spectroscopic measurements.

IN recent years much attention has been focusedon the synthesis of compartmental ligands

capable of bringing two, or more metal atoms intoclose proximity>". The impetus for this work hasmainly come from a requirement to understand thenature of magnetic interactions present in oligo-metallic clusters. Besides, bi- and poly-metallic com-plexes might have profound catalytic activity. OUf

earlier work on the metallic complexes, of 3-formyl-salicylic acid and its schiff bases with mono- anddiamines led us to the realisation that each of theseligands, could in principle, form complexes witheither two identical metal atoms (homo binuclear)or to two different metal atoms (hetero binuclear=s).In fact, we have isolated and characterized severalhomo- and hetero-binuclear complexes with com-partmental ligands of the type (Ia) [3-fsaen(Hz)M,where R = -(CH2)2,3-fsatmda (H2)M, . whereR = -(CH2)3-, 3-fsaopda (Hz)M, where R=o-C6H4], where the two metals mayor may notcontain other ligands attached to them, dependingon the reaction conditions. Very recently, severalother workers have used 3-fsaen-H4 to synthesizehetero- and homo-binuclear complexes3,7-13 invol-

+Part I. Dey, K. & Maiti, R. K. Indian J. Chem., 14A(1976),602.