'iNH. The (NH) mode is observed at 1650. How-ever, in the spectra of the complexes, these bandsdisappear indicating the displacement of N-H hydro-gen by the metal ion. This is further confirmed bythe appearance of new bands around 540-510 in thefar infrared spectra of the complexes, assignable"to vM-N. A sharp band appearing at 1720-1700in the ligands may be assigned to 'iC=O whichappears at the same place in the spectra of the _com-plexes, ruling out the possibility of coordinationthrough carbonyl group. The ligand 2-mercapto-quinazol-4-one contains a thioamide group. Organiccompounds having a thioamide group (H-N-C=S)give rise8-IO to four thioamide bands in their IRspectra : thioamide band I around 1500, band IIaround 1400-1300, band III around 1000 andband IV around 700-850. These bands have contri-butions from (SC-H+SN-H), (vC=S + vC=N+~C-H),(SC-N + vC-S) and vC-S modes of vibrations,respectivelys-!", In the present Iigands, these bandsappear at 1540-1525, 1300-1280, 980-970 and 810-790. In the complexes, all the thioamide bandsexcept thioamide I, shift to lower wave numbers(-30-15 cnr-'). This fact indicates" the coordi-nation through sulphur. The bands observed inthe region 380-345 may be assigned? to vM-S.

Absorption bands indicating the presence of cyclo-pentadienyl group, are observed at -3000 (vC-H),-1440 (vC-C), ,....,1020-1015(S CH) and -840(~CH). All these bands correspond+ to those ofb~s(cycIopentadienyl)titanium(IV) dichloride andbls(cyclopentadienyl)zirconium(IV) dichloride. Thepersistence of the bands of cyclopentadienyl ringsIII the ~omplexes indicates that these groups remaindelocahzed and n-bonded to the metal and retaintheir aromatic nature.

On the basis of above discussion, it becomes evi-~ent that the present ligands act as bidentate chelat-mg agents, coordinating through thione sulphurand amino nitrogen. Thus, the structures (II) and(III) may be proposed for these complexes.

M Ti(IV) or zr(IV);/N) represents the anion"S

of ligands MQztR, PQztH and TQztR.The autho~ are thankful to Prof. R. P. Rastogi,

~ead, Cheml~t~y Department, Gorakhpur Univer-srty, for providing the necessary facilities.

References1. PRIm, C. & Tost, G., Aust, J. Chem., 29 (1976), 543 j Can.

J. Chern•• 54 (1976), 158.

NOTES

2. Rw>IJK, J., J. inorg: nucl. Chem., 35 (1973), 239.3. GAJENDRAGAD, M. R. & AGARWALA, U., Aust, J. Chem.,

28 (1975), 763.4. CHUDY, J. C. & DALZIEL, J. A.W ., J. inorg, nucl. Chem.,

37 (1975), 245.5. WILKINSON, G. & BIRMINGHAM, J. M., J. Arn. chem. Soc.,

76 (19)4),42&1.6. DAVE, G. R., J. Indian chem. Soc., 37 (l960), 595.7. ADAMS, D. M., Metal-ligand and related vibrat ons (E.

Arnold, London), 1967.8. SINGH, B., LAKSHMI & AGARWALA, U., Inorg, Chem., 8

(1969), 2J41; SINGH. B. & AGARWALA, U., J. i norg, nucl,Chem., 31 (1969),2575.

9. DWIVEDT, J. S. & AGARWALA, U., Indian J. Chem., 10(1972), 652.

10. SINGH, B. & THAKUR, K. P., J. inorg, nucl. Chem., 36(1974), 1735.

11. FRITZ, H. P., Advan. organomet, Chern.. 1 (1964),262.

Dithiophosphinates of Platinum Metals

R. N. MUKHERJEE· & V. S. VIJAYA

Indian Institute of Technology, Bombay 400 076

Received 3 August 1981; revised and accepted 21 October 19&1

Dlthlophosphlnates of Ru(UI) and Os(IIT) have been preparedand their ESR studies indicate distortion from octahedralgeometry. Wherever possible the spectrochemical and nephe-lauxetic parameters have been evaluated for the correspl>lldi~Rh(llI), 1r(1II), Pd(lI) and Pt(lI) complexes.

UNLIKE metals of the first transition seriesv", thedithio complexes of osmium have received much

less attention, The magnetic, spectroscopic and ESRstudies of osmium(III) dithiophosphinates are re-ported in this note. The corresponding complexesof ruthenium(III) and other platinum metals areincluded for comparison.

The dark brown tris[di(2-methyl-5-chloro-phenyl) dithiophosphinato]osmium (III) complex,OsMeCldtpi)a and the corresponding p-tolyl analo-gue, Os/Medtpi), were prepared by reacting (NH4)2-OsCI. and sodium salt of the ligand. The requiredcomplexes were recrystallised from methanol-chloro-form mixture. By refiuxing (NH4)zOsCI. and PPhain decanecontainingconc. HCl for 16hr, Os(PPh3)3C1awas obtained which on reaction with sodium salt ofthe ligand gave a brown complex [Os(Medtpi)z(PPh3)2]CI. The complex [Os(MedtpiMo-phen)]CIwas similarly obtained from Os(phen)2CI3' Thecomplexes of ruthenium, rhodium, iridium and palla-dium were prepared by refiuxing the ligand and metalchloride in methanol, while K2PtCI4 was used for thepreparation of the platinum complex. The analyticaldata are given in Table 1.

The dithiophosphinic acids were prepared by amethod described in the literature",

The brown complex Ru(MeCldtpi)a exhibited ad-d band at 19000 crrr+, while the other bands (22000and 16400 em-I) were assigned to charge transfer

421

INDIAN J. CHEM., VOL. 21A, APRIL 1982

10. BoYD, S. A., KOHRMAN,R. E. & Wr:sr, D. X., J. inorg.nucl. Chem., 38 (1976), 1605.

11. ADAMS, D. M., Metal-ligand and related vibrations (St.Martin Press, New York), 1968.

12. NElSON, W. H., Inorg, Chem., 6 (1967), 1509; PELIZZIC. & PELIZZI, G., Inorg, chim, Acta, 18 (1976), 139. '

13. TANAKA, T., KUMURA, M. & OICAWARA,R., J. organa-metal. Chern .• 1 (1964), 484.

All the complexes were prepared by a generalprocedure briefly described below.

The appropriate 2-mercaptoquinazol-4-one (lor2. mol) .was. added to .a solution of bis(cyclopenta-d!enyl)t~tanll~m(lV) dichloride or bis(cyclopenta-dienyljzirconium/lv) dichloride (1 mol) in anhy-drous tetrahydrofuran (50 ml) and the reaction mix-

. ture .W!HL_rf'.fIIIYf'i/ Pur.lntinn "I' h"Ap"'n6~ ~t.I~_:A_

INDIAN J. CHEM., VOL. 21A, APRIL 1932

lODQ (23400 em-s) value for Ir(I1I) analogue wasfound to be higher, the B. f1 and Z* values viz. 181cm=, 0.27 and 0.017 respectively were smaller,showing the increased covalency of the iridium com-pound compared to the rhodium derivative.

Pd(MeCldtpi)2 and Pt(MeCldtpi)2 were found tobe diamagnetic indicating square planar geometryaround the central metal atom and their electronicspectra showed bands around 21200 and 23200 cnr-'respectively, which were assigned to d.,'J_t/2_ d~.,transition. Using equations given elsewhere! the IOD.(23300 and 25300 cm-") values were evaluated andare consistent with the lower position of dithiophos-phinates than dithiophosphates and dithiocarbama-tes in the spectrochemical series.

TABLE 1 - ANALYTICALDATA OP THE Q)MPLEXE'3

Found (calc) (%)Compound

C H S

Ru(MeCldtp i), ~4.00 3.12 16.86

Os(MeCld tpi),e~··~i) (3.17) (16.90)~'().3O 7..".$ 15.21

Os(Medtpi),(41.14) (2.9-~) (15.67)~.6.97 3.89 18.48

[Os(M edtpiMPPh3)~]a(1'.9.G~) (4.11) (18.81)n.(/I 3.10 8.56

(Os(Medtpi).(o-phen)jCI(75.4<;') (3.30) (9.82)

50,11, 3.20 13.20

Rh(MeCldtpl),(51.95) (3.~.6) (13.85)~.3.6,) 3.7..1, 16.&4

Ir(MeCldtpi)3(".1' •.2<;') (3.16) (16.87)42.0) 2.6& 15.62

Pd(MeCldtpi).(41.08) (2.93) (15.65)41.6~ 2.95 15.88

(".2.]<;') (3.01) (16.07)Pt(MeCldtp i). 36:80 2.80 14.52

(37.97) (2.71) (14.46)

TABLE2 - ESR DATA FORRu(lIl) AND Os(Ill) COMPLEXES

Compound gl g. g. All A,1

Ru(MeCldtpi), 2.1096 2.0335 1.9777Os(MeCldtpi), 2.0542 2.0190 1.9386Os(Medtpi). 2.0594 2.00G8 ] .9646Os(Medtpi).(PPh.).C1 2.3675 2.0594 1.9959Os(Medtpi).(o-phen)CI 2.3589 2.2524 2.00w

36 2S

A values are given in Gauss.All spectra were recorded at 77°K

transitions. The low magnetic moment (I. 76 B. M.)may be due to the distortion of the complex-, Thiswas confirmed from ESR studies which showedthree g-values, as given in Table 2. On the high fieldside the hyperfine lines were resolved whereas on thelow field side the hyperfine lines were not resolved.The spectra of the dark brown Os(MeCldtpih andOs(Medtpi)3showed L_M charge transfer transitions-around 22500 and ]5000 cnr-', while a relativelyweaker band at 17000 crrr-' might be due to d-dtransition. The magnetic moments were around1.7 B. M. The ESR spectra gave three distinct s-values indicative of low symmetry distortion. It isknown that the g-values of complexes of the secondand third transition series elements are very sensitiveto the environments and changes were observed onaltering the donor sites from OsSa to OSS4P2andOSS4N2 by forming complexes with triphenylphos-phine and o-phenanthroline and their electronicspectra showed bands around 22000 and ]8000 crrr-'.

The brown diamagnetic Rh(MeCldtpi}:J showedbands around 23250 (lA]/I-IT~rT) and 19600 cnr+(lAlrT _IT],) in the electronic spectrum from whichthe spectrochemical (10Dq,20500 em-s), Racah inter-electron repulsion (B. 228 cm-l) and the nephelauxetic(~, 0.32) parameters were calculated. The B valueis of the order of 32 % of the free ion value (720 cm-")which indicates the high nephelauxetic effect of thesulphur ligands. This is also reflected by the effectivecationic charge (Z* = 0.074), while the corresponding

428

References1. MUKHERJEE,R. N., VENKATESHAN,M. S., ZINGDE, M. D.

& DHINGRA, M. M., J. inorg. nucl. Chem .• 38 (1976),634.

2. MUKHERJEE,R. N., VENKATESHAN.M. S. & ZINGDE,M. D.,J. inorg, nucl. Chem., 36 (1974), 547.

3. HIGGINS, W. A., VOGEL,P. W. & CRAIG, W. G., J. Am.chem, Soc .. 77 (1955), 1861.

4. HEATH, G. A. & MARTIN, R. L., Aust. J. Chem., 23(1970),1721.

5. DESIMONE,R. E., J. Am. dum. Soc .• 95 (1973). 6238.6. SHUPAK,S. I., BILLIG,E., CLARKE, R. J. H., WILLIAMS,R.

& GRAY, H. B., J. Am. chem. Soc .• 87 (1964).4594.

Complexes of Indium(Ill) Perchlorate

MARGUERITEA. WASSEF·& S. AHMEDDepartment of Chemistry, University College for Women,

Ain Shams University, Cairo, Egypt

Received 18 June 1981; revised and accepted 21 September 1981

Complexes of indium(lII) perchlorate with some nitrogen,oxygen and phosphorus containing Iigands like 4,4' -dimethyl-2,2' -bipyridyl, 2,9-dimethyl-o-phen3"lthroIine, tripyridyJ,pyridine N-oxide, diphenyl sulphoxide and bis(diphenylphosllhine)-methane, -ethane and their oxides have been prepared andcharacterised on the basis of analytical, conductance and spectralstudies. The complexes are slx-eoordlnated with 4,4' -bipy,DM-o-phen and tripy. However, four-coordinated co:llJ)lexesare obtained with Py N-oxide, Ph$O and the liga!lds derivedfrom diphenylphosphine.

INDIUM(III) perchlorate hydrate reacts with avariety of nitrogen donors to give adducts of the

type [InL3](CI04b where = L= bipyridyl, o-phenan-throline and ethylenediamine'. A number of additioncompounds of indium perchlorate with oxygen donorshave also been reported 2-6. These complexes involvesix-coordinated indium(III), but the productobtained with triphenylphosphine oxide is reported tohave structure of the type In(Ph3 POMC104h7,8 withcoordination number four. Similarly, coordinationnumber four is shown in complexes with triphenyl-phosphine and triphenylarsine, In(Ph1P).(CI04h andIn(Ph3As).(CI04)a, respectively", In view of thisinteresting and varying behaviour of indium(IIl) to-