Anand, B. N.

Kapoor, R.

Paul, R. C.

English

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R C. PAUL,B. N. ANAND& R KAPOORDepartmentof Chemistry,PanjabUniversityChandigarh160014Received3 March 1976;accepted3 June 1976Synthesisof SubstitutedDimethylformamidylTe(IV) & Se(IV) ChloridesIN continuation of our earlier report! on thepreparationof alkali metal dimethylformamidyls,we now report the preparation and characterizationof substituteddirnethylformamidylcompounds,TeC13-CON(CH3h·DMF ard SeC13CON(CH3)2of Te(IV)and Se(IV) chlorides.Preparation of TeCt3CON(CH3)2.DMF (I) - Onstirring an equimolar mixture of TeC14and NaCON(CH3)2in CC14for 7-8 hr, a dark brown volumiJ1.oussolid separated which ',\0as filtered, washed withSubstitutedimethylformamidyltellurium(IV)chlo-ride[TeCI3CON(CH3)••DMF]andselenium(IV)chloride,SeCI3[CON(CH3).] havebeenpreparedby thereactionof TeC14andSeCl4with dimethylformamidylsodium.The compoundshavebeencharacterizedon thebasisof elementalanalyses,molar conductanceand IRspectraldata.(R=isonicotinyl)i INDIAN J. CHEM., VOL. 15A,JANUARY 1977Mi$d stereochemistry (Oh+D4h) was proposed Oneof the authors (RB.S.Y.) is thankhl tc (SIR,for ]'(II) complexes on the basis of magnetic New Delhi, fer financial assistance.marne t data. The electronic spectra of these R Ge.erencescamp xes show bands at about 10·00, 14·8 and23'5 K characteristic of an octahedral gecmetry. 1. AKBARALl, M. & LIVINGSTONE,S. E., Coord. Chem.Th k .. b d h t" f N'(II) . Rev 13 (1974)10e ea mtensIty. an c arac ensilc 0 I III 2. KOR~~I,J., Egy~suliGyogyszeres Tapszergyar(Hung.),squar planar envIronment appears to have sub- 148(1962),949.merg in thestrongintensity '.12 bandof cctahedrally 3. FIGGIS,B. N. & LEWIS,J., citedin Moderncoordinationcoord nated Ni(II). chemistry,/ditedby J. Lewis& R G. Wilkins(Inter-Th 22·22 and 15·87kK bands in the spectra of SCIence,NewYork), 1962.C (IP SC H)Cl d C (IPTSC 2H) . d' t 4. KENT,BAREFIELD,E. BUSCH,D. H. & NELSON,S. M.,u -. an . u - III Ica e squ~re Q. Revs.,22 (1968),457.plana and hIghly dIstorted octahedral geometnes 5. KANEKAR,C. R & CASEY,A. T., ]. inorg.nucl. Chern.,respe4tivelyfor the two complexes. 31 (1969),3105.! 6. DRAKE,J. E., VEBRIS,J. & WOOD,J. S., ]. chem.Soc.,I R _ NH _ NH _ CS_ NHPh (A), (1968),1000.I 7. KUSKA,H. A. & YANG,P. H., Abstractof the5thCentralRegional Meeting of the American ChemicalSociety,Cleveland,Ohio, 13-15May 1973.8. STOKLOSA,H. J., WASSON,J. R & CORMIC,J. Me.,Inorg.Chem.,13 (1974),592.9. SINGH,P. P. & RIVEST,R, Can. ]. Chem.,46 (1968),2361.10.NAGANO,K., KINOSHITA,H. & HIRAKAWA,A., Chem.Pharm. Bull., 12 (1964),1198;1207.11.DUTT,N. K. & CHAKDER,N. C., J. inorg. nucl. Chem.,32 (1970),2303.12.BRAIBANTI,A., DALLVALLE,F., PELLINGHELL,M. A. &LAPARATI,E., Inorg. Chem.,7 (1968),1430.13.CORMIC,B. J. Mc.,BOZIS,R A., Inorg. Chem.,10(1971),2806.14.MATHEW,M., CARTY,A. J. & PALENIK,G. J., J. Am.chem.Soc., 92 (1970),3197.15.ESKENAZI,R, ROSKOWAN,J. & LEWITUR,R, ]. inorg.nucl. Chem.,28 (1966),521.16.SPECA,A. N., KARAYANIS,N. M. & PYTLEWSKI,L. L.,Inorg. chem.Acta, 9 (1974),87;]. inorg. nucl. Chem.,36 (1974),3751.17.TEOTIA,M. P., RASTOGI,D. K. & MALIK,W. R, Inorg.chim. Acta, 7 (1973),339.18.BEECROFT,B., CAMPBELL,M. J. M. & GREZESKOWIAK,R, J. inorg. nucl. Chem.,36 (1974),55.19.BROWALL,K. W. & INTERRANTE,L. V.,]. Coord.Chem.,3 (1973),27.20.MASSACEST,M. & PONTICELLI,G., ]. inorg.nucl. Chem.,36 (1974),2209.A ~egative shift in v(N-H) bands in all thecomptexesexcept in the caseof VO(IPTSC-2H), ascomp redwith the solution spectrum(in acetonitrile)of th ligand indicates the involvement of at leastone 0 th )N -H groups in b nding. The amide-Iband! suffers a negative shift in the spectraof th~ adducts as ccmpared with the free ligandand disappears in the spectra of condensaticncomp£unds, indicating the involvement of the)C=? group of he ligand in coordinaticn inthe a~ductsand the destructicn of this grcup pre-SUma ly via enolization in the latter ccmplexes.A ositive shift of about 30 cm-1 in the ringvibr ion in the spectraof the adductsand of about60 ct-1in those of condensation c(jmpounds ascomp red with the solution spectrum of the parentligan suggeststhe involvement in coordination ofthe c~rb()nyloxygen in the adducts and carbcnyloxyg$ as we l aspyridine nitrogen in the latter10.Th~ v(C=S+C-N) modell is either very weakor difappears completely in the spectra of con-densa ion products M(IPTSC-2H) [M=VO(IV),Co(II , N.i(II) and Cu(II)] but shifts to the higherfrequ ncy side in the sp ctra of t e adducts such asVOS~4.IPTSC' CoC12.IPTSC, Ni(IPTSC-H)Cl andCu(I' TSC-H)Cl indicating the destruction of thethiok to group in the former complexes and non-parti ipation of the )C=S group in the lattercomp~exes.Th~ positive shift in the v(N-N) mode in thespectta of all the complexesindicates the involve-mentlof one or both of the nitrogens in bondingI2.Th lower value of v(V-=O) in VO-IPTSC Cf m-plexe~ as compared with a number of VO(IV)comp.exes13,I4m y be due to the existence ofV=q- - -V interaction. This is in accord withthe s~normal magneticmomentsof theseccmplexesdiscu sedearlier. The bandsat 1100-1125,1025and975 -1 in the spectrumof VOs04.IPTSC may beattri tited to the chelatingsulphatogroup15.Th l w frequency bands in 435-390and 308-292cm-1~egionsin all the IPTSC complexesare ten-tativ¢ly assigned16•17to v(M-O) and v(M-N)(ref.• 6, 18) modesrespecti ely. The 384-368cm-1regio* band in theunchargedcnmplexesand 342-333cm-1fgion bandin CoCl2.IPTSC and Cu(IPTSC-H)Clmay e attributed to v(M-S) (ref. 19) and v(M-Cl)(ref. I 0) modes respectively.52 II~ INOTESTABLE 1- ANALYTICAL DATA OF THE COMPOUNDSm.p.Found (%) (calc.)(0e) MClC HNTeClaCON(CHa).·DMF100-10232-928·017'93·3H(33-628'19)TeClaCON(CHa).·Q19529·061-86,029,24 436· )Se laCON( 2 29·6,540-65 500741·3-CCI, and dried. Sodium chloride formed andany unreactedNaCON(CHs)2were removedbytreatingthe solid with DMF. The DMF solutionon evaporationunder reducedpressureyieldedamustardcolouredpowderanalysingfor TeClsCON(CHS)2.DMF. Compound(I) is insolublein CCI,and benzenebut soluble in methylenechloride,nitrobenzeneand nitromethane.The suspensionof I in CCI, on refluxingwithquinoline(Q) yieldeda whitesolid,TeClsCON(CHsh.Q, insolublein CCI" benzeneaT'.dslightly solubleinmethylenechloride,nitrobenzeneandnitromethane.Preparation of SeClaCON(CHsh (II) - It waspreparedin a manneranalogousto compound1.However,the separationof NaCI and unreactedNaCON(CHa)2couldnot be affectedby treatmentwith DMF, as the compounddisproportionatedtogive elementalSe. The compounddissolvedinmethylenechlorideon prolongedstirrir.g ap.din-solubleNaCI and NaCON(CHa)? were removedbyfiltration. The solution on evaporationup.derreducedpressureyieldeda yellowsemi-solid,SeClsCON(CHs)2'This compoundis solublein methylenechlorideand slightly solublein CCI" nitrobenzeneand nitromethane.The analyticalresultsaregivenin Table1. Allthesecompoundsarehighly sensitiveto moisture.Solvolyticreactionsof metalhalidesdo not takeplacein DMF due to the very low acidityof theproton on DMF. However,such reactionsmaybecarriedout by reactingmetalhalideswith alkalimetal dimethylformamidyls.The reactionsmaybe visualizedas:MC1,+NaCON(CHa).--+MClaCON(CHa).+NaCl(M~Te or Se)Molar conductivitiesof the millimolarsolutionsof compoundI (23 ohm-1cm2mole-I)and of itsquinolineadduct(22 ohm-1cm2mole-I)in nitro-benzeneindicatethattheybehaveas1:1electrolytesin this medium2.Molecularweightof I as deter-minedby freezingpoint methodwas foundto be192(averageof threemeasurements)whichis aboutone-halfof the requiredvalueof 379. The mole-cularweightof the quinolineadductcouldnot bedetermineduetoitslimitedsolubility. The~eobser-vationscanbeexplainedin termsof Eqs. (1)and(2).Equilibrium(1) canbe justified,if it is assumedTeClaCON(CHsla.DMF--+[TeCl.CON(CHa)•.DMF] +Cl- ...(1)TeClaCON(CHa).·DMF--+TeClt0- 0[CHa' I II /CHa]+ ./"-N-CH-C-N, ...(2),,-CHathat Cl- ion and[CON(CHsh]-ion havesimilarelec-tronegativities.The otherpossibilityis the ioniza-tion of solvatedformamidylanion (Eq. 2). Theexistenceof thisanionin theformof its alkalimetalsaltshasbeenearlierproposedby Brederecket al.3.Molarconductivityof the millimolarsolutionsofcompound(II) in nitrobenzene(7ohm-lcm2mole-I)showsit to be a non-electrolyte.Mol wt of thecompounddeterminedby freezingpoint method(255)tallieswith the formulaweight(257).The 1R spectraof the compocrJd(I) and of itsquinolineadductshowintenseband at 1640cm-1which may be ~signed to vC=O. Thesecom-poundsalso~howmediumintensitybandat 370cm-1whichis characteriEticof Te-Cl bondin compoundscontatainingTeC1;cation'. The1Rbandsat 1630s,1580mand1505min purequinolinedue to vC:.:.: Cand vC ~ N are shiftedto higherfrequencyregionin the addLct(1635m, 1590s and 1555m). Thisindicatestheexistenceof coordinatedquinoline,inagreementwithourearlierworkli. The1Rspectrumof seleniumcompound,(II) could not be recordedas it will not formmullwith nujol and it reactedwith KBr and Cs1plates.Thermalbehaviourof I aswellasof its quinolineadductshowsthatthesedecomposefinallytobeTe02through the formation of some unstableinter-wediates.Fromthetotallossin \\'eightthecomposi-tionofthecompound\\'aschecked. Thecompositionof the intermediateproductscould not be ascer-tained.References1. PAUL,R. C., ANAND,B. N. & KAPOOR,R., Indian J. Chem.,13 (1975),1338.2. CARTY, A. J., Can. J. Chern.,45 (1967),345.3. BREDERECK,H., EFFENBERGER,F. & GLEITER,R., Angew.Chern.,4 (1965).951.4. HAYWARD, G. C. & HENDRA, P. l,J. chern.Soc., (A)(1967),643.5. PAUL, R. C., (Miss) KHURANA,H., VASHISHT,S. K. &CHADHA,S. L., Z. anorg.aUgen.Chern.,370(1969),185.Compoundsof Thallium(III) ChloridewithSomeLewis AcidsK. C. MALHOTRA& BALKRISHANDepartmentof Chemistry,Himachal PradeshUniversitySimla 171001Received31 January 1976;accepted4 June 1976A numberof adductsof thallium(III)chloridewithLewisacidshavebeenisolated.On thebasisof con.,ductance,molecularweightandIR data,theadductswithphosphoruspentachloride,iodinetrichlorideandtetrachloridesof seleniumand telluriumhavebeenformulatedas PCI:.T1C1.,ICI;.TICI4and MCI;.TICI,·respectively;but in thecaseof trichloridesof phos-phorus,arsenicandantimony,the adductsobtainedhave beencharacterizedas halogen-bridgedfour-coordinatedTI(III) compounds.

Synthesis of Substituted Dimethylformamidyl Te(IV) & Se(IV) Chlorides

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Synthesis of Substituted Dimethylformamidyl Te(IV) & Se(IV) Chlorides

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