Sandhu, S. S.

Singh, Tarlok

English

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3. DALZIEL, J. A. W., HOLDING, A. F. LE C. & W.UTS, B. E.,J. che ni. Soc., A (1967), 358.4. MALHOTR.\, K. c.. Indian J. Chem., 12 (197+), 823.5. NEGOn;,M.& SP.\CU, P., Chern. Abstr., 75 (1971), 117880b6. :KICPON, P. & MEEK, D. W.,j. Am. chem, Soc., 87 (1965),4951.7. KING, 1\1.G. & ~fCQUILLA~, c. P., J. chem. Soc., A,(1967), 898.8. SLINKARD, W. E. & MEEK, D. W., Inorg, Chem., 8 (1969),1811.9. \VHEATLAND, D. A., CLAPP, C. H. & WALDRON, R. W.,Inorg, Chem., 11 (1972), 2340.10. NICPON, P. & MEEK, D. W., Inorg. Synth., 10 (1967),157.11. SANDHU, S. S. & SINGH, TARLOK, Transition met. Ch.m., 1(1976), 155.12. SLINKARD, W. E. & MEEK, D. 'vY, J. chem. Soc. DaltonTrans. (1973), 1024.13. TIETHOF, J. A., HETEY, A. T. & MEEK, D. W., Inorg.Chem., 13 (1974). 2505.14. FERRARO, J. R., Low-frequency vibrations of inorganic6- coordination compounds (Plenum Press, New York),1967, 111, 247.15. ADAMS, D. M., Metal-ligand 6- related vibrations (EdwardArnold, London), 1967, 26, 316.16. COATES, G. E. & RIDLEY, D., ]. chem. Soc. (1964), 166.17. STRmnfEN, D. P.,]. inorg. nucl. Chem., 37 (1975)' 487.18. CLARK, R. J. H. & WILLIAMS, C. S., Inorg. Chem., 4(1965), 350.19. CLARK, R. J. H. & DUNN, T. M.,]. chem, Soc. (1963),1198.20. SABAKINI, A. & SACCONI, L., J. Am. chem. Soc., 86(1964). 17.Ligating Properties of Tertiary Phosphine!Arsine Sulphides or Selenides: Part IV-Complexes of Ditertiary Phosphine Disulphides& Diselenides with Cadmium(II) HalidesS. S. SANDHU & TARLOK SINGHDepartment of Chemistry, Guru Nariak Dev UniversityAmritsarReceived 6 July 1976; revised 2 March 1977;accepted 18 May 1977Ditertiary phosphine disulphides and diselenides forrnt :1 (metal-ligand) adducts of the type CdX2 (L-L){whereX=CI, Br and I; L-L=I,2-ethylenebis(diphenyl-phosphine sulphide or selenide) (EDPS or EDPSe);1,3-propylenebis(diphenylphosphine sulphide or sete-nide) (PDPS or PDPSe); 1,4-butylenebis(diphenyl-phosphine sulphide or selerride (BDPS or BDPSe) and1,6 - hexamethylenebis(diphenylphosphine selenide)(HDPSe)]. A 2: 1 adduct, Cd2X~BDPSe,has also beenprepared. The adducts have been characterized onthe basis of elemental analyses and infrared spectraand have been assigned tetrahedral bridged struc-tures.VERY few adducts of Cd(II) with tertiary phos-phine sulphides or selenides are reported inliterature as compared with those of other class bmetal ionsl~J2. In the present note we are reportingadducts of ditertiary phosphine disulphides ordiselenides with Cd(II) halides.The ligands, 1,2-ethylenebis(diphenylphosphinesulphide or selenide) (EDPS or EDPSe), 1,3-propyl-enebis(diphenylphosphine sulphide or selenide)(PDPS or PDPSe), 1.4-butyl'nebis(diphenylphos-phine sulphide or selenide) (BDPS or BDPSe) andNOTES1,6-hexamethylenebis( diphenylphosphine selenide)(HDPSe), were prepared by procedures analogousto those reported in literature8,l3. The analyticaldata for the ligands have been already reported=,The adducts were isolated by mixing the hotsolutions of the ligands in benzene or ethanol withthose of cadmium(II) halides in ethanol. Thewhite solids obtained after either scratching orrefluxing were filtered and washed with warmethanol or benzene and dried in vacuo. The ele-mental analyses for the adducts (Table 1) werecarried out by the Australian MicroanalyticalService, Melbourne. The infrared spectra in therange 4600-200 crrr- were recorded using Specord71 IR and Beckman IR-12 spectrophotometers.Infrared spectra indicate that the vP-C (aromatic)modes occurring in the ligands EDPS, PDPS,BDPS, EDPSe, PDPSe, BDPSe and HDPSe res-pectively at 1090, 1080, 1090, 1090, 1080, 1080and 1100 crrr! remain practically unaffected aftercomplex formation.The vP=S modes decrease by 38-53 cnr< whilevP=Se modes decrease by 10-16 crrr! after co-ordination to Cd(II). However, the vP=Se forCdX2'PDPSe remains practically unchanged. Theseobservations are in agreement with similar changesreported in literature8-11,l,. Further, vCd-Cl occursat 266 crrr+ in CdCl2·PDPSe and 274 crrr" in CdCI2•PDPS which is very strong in intensity. Thismay be rlue to overlapping with vCd-S as therange for the latter bands is 236-74 crrr", vCd-Brand vCd--Se occur in the ranges 215-225 and 240-262 em"! respectively. vCd-I and frequenciesdue to bridging halogens fall below 200 crrr+ (ref.16-20).All the adducts have been assigned tetrahedralstructures. Structures of types I and II may beassigned to the 1: 1 and 2: 1 (metal-ligand) com-plexes.X L""'Cd ••••.•••.•.'x .•.•..••... ~LIL X L'-......Cd~ ~Cd""""'"X./" ~x~ <,xlrIn the BDPSe adduct with CdBr2 the ligandhas been found to act as a bridge between the twometal ions. The bridging behaviour of the ligandis evident from the fact that there is no increasein the number of -CH2- (bending) bands in theIR spectrum of the complex. The other alter-native, chelate formation, would lead to the lower-ing of the symmetry of the ligand and hence anincrease in the number of bands due to -CH2-(bending). Also, on chelation, high membered ringswill be formed which are less stable.One of us (T.S.) is grateful to the CSIR, NewDelhi, for the award of a fellowship. We are alsoindebted to the authorities of the Regional Sophisti-831INDIAN J. CHEM., VOL. 15A, SEPTEMBER 1977ComplexTABLE 1 - MELTINGPOINT ANDANALYTICALDATAOF CADMJUM(II)HALIDE ADDUCTSFound (Calc.), % m.p.(OC)CdCl •.PDPSCdCl2·PDPSeCdBr z-PDPSCdBr a-EDPSeCdBr •.PDPSeCd.Br4·BDPSeCdBr2·HDPSeCdl s-EDPSCdl2·BDPSCdl s-PDPSCdI2·EDPSeCdI2·PDPSeCdl s-BDPSeC49'09 (49'15)43·28 (43-03)43·86 (43'18)37·78 (37'70)38·85 (38'48)30'77 (29'79)41·86 (40'70)37·59 (37'70)40·72 (39'25)39·15 (38'48)34'52 (33'80)36·15 (34-61)36·24 (35'37)H4-14 (3,94)3-69 (3045)3·82 (3047)2'95 (3,00)3·21 (3,09)2-66 (2'48)3-69 (3-60)2·87 (3'00)3·51 (3'27)3·15 (3'09)2-67 (2-60)3'50 (2'78)3'18 (2'95)PIS10'6(S) (9'71)7'20(P) (8'52)8'2(S) (8'55)7'8(P) (7'7)7'20(P) (7'36)5'5(P) (5'5)6'3(P) (7'0)7'7(P) (7'7)6'7(S) (7048)6'5(P) (6'70)5'6(P) (6'62)6'5(P) (653)22S(d)240228-30232(d)250(d)275(d)75(d)250-52240(d)242-44260(d)275(d)265 (d)cated Instrumentation Centre, IIT, Madras, for re-cording far infrared spectra in the range 650-200 cnr+.References1. BANNISTER,E. & COTTON,F. A·,I chem.Soc. (1960),1959.2. NICPON, P. & MEEK, D. W., Chem. Commun. (1966),398.3. VEER, W. & JELLINEK, F., Reel. Trau. chim: Pays-Bas.Be/g., 85 (1966), 842.4. DALZIEL,J. A. \V., HOLDING,A. F. LE C. & WATTS, B. E.,I chem. Soc. (A) (1967), 358.5. MALHOTRA,K. c., Indian I cu«; 12 (1974), 823.6. NEGOJU,M. & SPACU,P., Chem. A bstr. , 75 (1971), 117880b.7. MEEK,D.W. &NICPON,P.,I Am. chem, Soc., 87 (1965),4951.8. KING, l\1. G. & MCQUILLAN, G. P., I chem. Soc. A(1967), 898.9. SLINKARD,W.E. &MEEK,D.W.,Inorg. Chem.,8 (1969),1811.10. SLINKARD,W. E. & MEEK, D. W., I chem. Soc., DaltowTrans. (1973), 1024.11. WHEATLAND,D. A., CLAPP, C. H. & WALDRON, R. \\T.,Inorg. Chem., 10 (1972), 2340.12. KING, M. G., MCQUILLAN,G. p. & MILNE, R., I inorg.nucl, Chem., 35 (1973). 3039.13. NICPON, P. & MEEK, D. W., Lnorg. Synth., 10 (1967), 157.14. SANDHU, S. S. & SINGH, T., Transition Met. cu-«, 1(1976), 155.15. TIETHOF, J. A., HETEY, A. T. & MEEK, D. W., Inorg,Chem., 13 (1974), 2505.16. ADAMS,D. M., Metal-ligand &- related vibrations (EdwardArnold, London), 1967, 26, 316.17. FERRARO, J. R., Low-frequency tnbrations of coordinationcompounds (Plenum Press, New York), 1971, 111, 247.18. COATES,G. E. & RIDLEY, D., I chem. Soc. (1964). 166.19. CLARK, R. J. H. & WILLIAMS, c. S., lnorg. cu«, 4(1965), 350.20. CLARK,R. J. H. & DUNN, T. M·,I chem. Soc. (1963), 1198.Complexes of 2-Antino-5-phenyl-l,3,4-thiadia-zole with Cu(II), Ni(II), Co(II), Fe(lI) & Zn(lI)SulphatesN. B. SINGH & l SINGHChemistry Department, Gorakhpur University, CorakhpurReceived 10 January 1977; accepted 16 April 1977Complexes of Cu(I1), Ni(II), Co(II), Fe(II) and Zn(II)sulphates with 2-amino-5-phenyl-l,3,4-thiadiazole havebeen prepared and characterized on the basis of ana-lytical, magnetic susceptibility, infrared and electronicspectral, TGA, DTA and DTG data. The ligand showsbidentate behaviour in all the complexes except in thecase of Ni(lI) complex where it acts as a monodentateligand. All the complexes reported have octa-hedral stereochemistry except [Cu(2-amino-5-phenyl-1,3,4-thiadiazole)2]SO, which is square-planar.832THE ligand, 2-amino-5-phenyl-l,3,4-thiadiazole (I)has four potential donor sites, viz. three nitrogenatoms and one sulphur atom. It will therefore be?f interest to investigate the nature of bondingIII the complexes formed by 2-amino-5-phenvl-1,3,4-thiadiazole. In this note, we report t-heresults of our studies on the Cu(II), Ni(II), Co(II).F e(II) and Zn(II) sulphate complexes.N---NII IIPh-C C-NH."'s/(I)All the chemicals used for the preparation ofthe complexes were of AR or chemically puregrade. The ligand, 2-amino-5-phenyl-1,3,4-thiadia-zole (hereafter denoted as APTH) was preparedbv the literature methods.- Th~ complexes were prepared by mixing aqueoussolutions of metal sulphate hydrates with the etha-nolic ~olution of liga~d in (1: 1) ratio and refiuxingthe mixture for 30 rmn, 1 hr , 2-3 hr in the case ofCu(I!); Ni(II), Co(II) and Fe(II) , Zn(II) com-plexes respectively. The complexes obtained werefiltered and washed with hot ethanol and waterand dried in vacuo.Elemental analyses and magnetic measurementswere carried out using standard methods. Electronicand IR spectra, TGA, DTA and DTG of complexeswere also recorded using standard methods.Th~ mol~cular formulae and the elemental analysesare grven III Table 1. On comparing the infraredspectra of the ligand with those of the complexes,It was found that the positions of most of the bandshad shifted. The asymmetric and svmmetric 'INHob.served at., 3350 and 3270 crrr" in the ligand .wereshifted to 3.)60-3430 and 3280-3330 crrr+ respectIvelyin the spectra of the complexes. 'IC-S observedat 648 cm-l in th.e ligand was shifted to a positionbelow 60~ crrr" I~ t~e spectra of the complexes.!hese . evidences indicate that the complexationIS taking place through the sulphur atom andnitrogen atom of the NH2 group.From the analytical data and molecular formulaeof the complexes, it is apparent that, in the case ofNi(II), the APTH behaves as a monodentate

Ligating Properties of Tertiary Phosphine/Arsine Sulphides or Selenides: Part IV - Complexes of Ditertiary Phosphine Disulphides & Diselenides with Cadmium(II) Halides

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Ligating Properties of Tertiary Phosphine/Arsine Sulphides or Selenides: Part IV - Complexes of Ditertiary Phosphine Disulphides & Diselenides with Cadmium(II) Halides

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