Chadha, S. L.

Gupta, P. K.

Paul, R. C.

Sharma, Pratibha

Singh, Harinder

English

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NOTESFrom the dataavailables.6in respectof nioximeand salicylaldoximeit can be concludedthat thechelatesderivedfrom the alicyclicligand are lessstablethan thosefromthe aromaticone. In otherwords,removalof conjugationin the ring systemofthereagentresultsin decreaseof thermalstabilityof its metal chelates. Similar observationsweremadeby Botteietat.7in theirstudieson 8-hydroxy-1,2,3,4-tetrahydroquinoline.Salicylaldoxime,resace-tophenoneoximeand 2-hydroxy-l-naphthaldoximeform six-memberedchelaterings with the metalbondedtophenolicoxygenandnitrogenoftheoximegroup. All the three oximesform 1:2 complexes(metal to ligand ratio) with the three metals.2-Hydroxy-l-naphthaldoximechelatesarethermallymorestablethan the correspondingsa1icylaldoximechelates. The enhancedthermalstability can beaccountedfor by the presenceof an additionalaromaticringSandconsequenthigherelectronden-sity at the reactivecentre. The higher thermalstability of resacetophenoneoximecomplexeswasascribedto the higher electrondensity at thereactivecentre9•Theauthorsarethankfulto theCSIR, NewDelhi,for theawardof a junior researchfellowshipto oneof them(RS.N.).References1. MICHIO MASHIMA,J. chem.Soc. Japan, 74 (1953),622.2. GUSEV, S. I.. KUMOV, V. I. & SOKOLOVA,E. V., Zh.analit. Khim., 15 (1960),180.3.SESHADRINAIDU, R & RAGHAVANAIDU, R, Indian J.Chem.,15A (1976),69.4. VOGEL,A. I., A textbookof quantitativeinorganicanalysis(Longmans,Green, London), 1961,480,497,512.5. LIPTAY, G., PAPP MOLNAR,E. & BURGER,K., J. inorg.nucl. Chem.,34 (1969),247.6. DUVAL, c., Inorganic thermogravimetricanalysis (Elsevier,London). 1953,236,259,347.7. BOTTEI, R. S. & O'REILLY, J. C., J. inorg. nucl. Chem.,30 (1968),1481.8. BOTTEI,R. S. & McEACHERN,C. P., J. inorg.nucl. Chem.,32 (1970),2653.9. SESHAGIRI,V. & BRAHMA]I RAO, S., Z. analyt. Chem.,262(1972).275.with triphenylarsineoxide. \iVe report here thereactionsof triphenylarsineoxide with the com-poundsSnCla(OR),TiCla(OR)andTiCI2(OR)2'Theproductsformedhavebeencharacterizedonthebasisof IR spectra.All manipulationsandreactionswerecarriedoutin anhydrousconditions.Tin(IV) chloride andtitanium(IV) chloridewere distilledprior to use.The alcoholsweredehydratedand distilledbeforeuse. Compoundsof the type TiCla(OR)werepre-paredby literaturemethods2-4andtheirpurity wasascertainedonthebasisof analyticalandm.p.data.The compoundsTiCI2(OR)s:i6and SnCla(OR).ROH7werealsopreparedby literaturemethods.The complexeswith triphenylarsineoxide werepreparedby mixing its solutionin chloroformordry ethanolwith the benzeneor ethanolicsolutionof TiCla(OR), TiCI2(OR)2or SnCla(OR).ROH. Asolidproductwasobtainedby keepingfor overnight.Thecomplexeswerefilteredunderanhydrouscondi-tions, washedwith benzene/ethanoland dried invacuo.TitaniumSand chlorine9were estimatedgravi-metricallyas titaniumdioxideand silver chloriderespectively.Analysesof the complexes(Table1) suggest1:1stoichiometry[alkoxide: (C6Hs)aAsO]forall of them.Limited solubilityof thesecomplexesin solventssuchas benzene,chloroformand nitrobenzenepre-cludesthecryoscopicdeterminationoftheirmolecularweightsand conductancemeasurements.Loweringof vAs=O of the pure ligand (880cm-1)to theregion825-855cm-1in thespectraof thecomplexesindicatesthe coordinationof its oxygento tin ortitanium. The shiftedvAs=O in thes,ecomplexesis quite close to the value reported for theSnCI4.2(C6Hs)aAsOcomplexIO• The vC-O modearisingfrom the C-O-M (M=Ti or Sn) moietyof the alkoxidepart in thesecomplexesis eitherpresentat thesamepositionat; in the caseof purealkoxideor is slightlyshiftedtowardshigherwavenumbersandthis is in accordwith thepresenceof""'''""\Ii*Titanium complexes are yellow solids, while the tincomplexesare white solids.tSatisfactory carbon and hydrogen analyses were alsoobtained for thesecomplexes.297-98295-96297-99288-89294-95290-91285-86298-300170195160209-11204-6ComplexTABLE 1- MELTINGPOINT AND ANALYTICAL DATA OF THECOMPLEXES*OF SnCI3(OR),TiCI.(OR) and TiCI.(OR). WITHTRIPHENYLARSrNEOXIDE (L)m.p. Found (calc.), %(DC) ~ _Metal CI9-43(9-44) 20'62(20'99)8'84(9'18) 21·20(20'42)8'38(8'61) 26·04(25'56)9,71(8'32) 17-79(18'50)9'89(9-52) 14·78(14'12)9-56(9'19) 21'37(20'42)7,60(7'98) 24·25(23'67)7·65(7-49) 11-02(11'11)20'38(20'52) 18·30(18'41)20·20(20'03) 17-80(17·97)19·85(19'57) 17·70(17'97)19'84(18'93) 22·04(22'64)18·52(18'36) 16'17(16·47)TiCI3(OCH3)·LTiCI3(OC.H5)·LtTiCI3(OC.H.CI)·LtTiCl3(OC.H.F 3).LTiCI.(OCH3).·LTiCI.(OC.H5).·LTiCI.(OC.H.CI) •.LTiCI.(OC,H.F3).·LSnCI3(OCH3)·LSnCI3(OC.H5).LSnCl3(OC3H~).LSnCI3(OC.H.CI).LSnCI3(OC.H.F3)·LTHE preparationandpropertiesof the complexesof triphenylarsineoxide with various metalhalideshavebeenwellstudied. However,verylittlework hasbeenreportedon the complexesof metalalkoxideswith donors1and of thesethereis noneComplexesof TriphenylarsineOxidewithTrichlorotin(IV) & Trichlorotitanium(IV)Alkoxides& Dichlorotitanium(IV)DialkoxidesComplexes of SnCI3(OR), TiCl3(OR) and TiCl.(OR).(where R=CH" C.H5' C3H~,C.H.Cl and C.H.F3) withtriphenylarsine oxide having 1: 1 stoichiometry havebeen prepared and characterized on the basis of ana-lytical and IR data.R. C. PAUL, PRATIBHA SHARMA,HARINDER SINGH,P. K. GUPTA& S. L. CHADHADepartment of Chemistry, panjab UniversityChandigarh160014Received19July 1976;accepted9 February 1977653,,*",.'•• " , "" rIIINDIAN J. CHEM., VOL. 1SA, JULY 1977IcoorPinatedalkoxygroupllin thesecomplexes.ThevTi+O vibrationis presentaround600-630cm-I inthes¢complexes.T~e empirical formula for the complexesSnQ3(OR),(C6H5hAsOuggeststhepossibilityof five-coorHinatedtin. Infraredspectraof thesecomplexessho~a broadbandof strongintensityin theregion510-~25em-I. Thisbandmaytentativelybeassi nedo, /~to tjheSn Sn vibration and such an asslgn-men~compareswell with a similar band presentin the region 480-530cm-I in the spectra ofSnCh(OR).R0H12and Sn(OR)2(acacH3.Thus thepres~nt1:1complexesappearto havealkoxybridgeddim~ricstructur~s.. The 1:2adductswithpyridineI4or ~-hydroxyqulJ1ollJ1eI5do not have such a bandwhiqhsupportsthe aboveview. v5n-Cl vibrationapp¢arsin the region310-320cm-1 and this valueis cljoseto thosereportedfor hexacoordinatedtinI6(d. pnC13-absorbsat 312em-I).T~e complexes TiC13(OR),(C6Hs)3AsOandTiClk(ORh(C6HshAsOmaybefive-coordinatedrnono-merfbutthis doesnotagreewiththeirinsolubilityincomfllonorganicsolvents. Alternativelythepresentcomplexesmay have six-coordinatedstructureacqijir d either by alkoxy bridgi g or chlorinbrid~ing. The IR spectrain the region 600-250cm-~is very complexand precludesascertainingofanybf theabovepossibilities.ThevTi-Cl vibrationin tbesecomplexesappearsin the region300-370cm-~and this is the region where uTi- Cl ofsix-doordinatedtitaniumalsoabsorbsl7.T~anksare due to the Head f the ChemistryDep~rtment,BanarasHindu University,Varanasi,for fhe far IR spectra.References1. llRADLEY, D. C., Progressin inorganicchemistry,Vol. 2i (Interscience, London). 1960, 303.2. YASTREBOV, V. V. & CHERNYSHEV, A. V., Zhur. obshch.I Khim., 40 (1970), 604.3. GLARK, R J. H., The chemistryof titaniumandvanadium,(Elsevier, London). 1968, 301.4. I'AUL, R C., SHARMA, P., GUPTA, P. K. & CHADHA, S. L.,Inorg. chim.Acta, 20 (1) (1976), 7.5. JlENNINGS, J. S;, WARDLAW, W. & "WAY, W. J. R,I chem.Soc., (1936), 637.6. PAUL, R c., GUPTA, P. K., GULATI, M. & CHADHA, S. L.,I leSS-COmmonMetals (communicated).7. BRADLEY, D. c., CALDWELL, E. V. & VVARDLAW, W'.,I chem.Soc., (1957), 3039.8. ERADLEY, D. C., HANCOCK, D. C. & VVARDLAW, W.,J. chem.Soc., (1952), 2773.9. VOGEL, A. I., A textbookof inorganicquantitativeanalysisi (Longmans, Green, London), 1961, 461.10. PHILLIPS, D. J. & TYREE, S. Y., I Am. chem.Soc.,83(1961). 1806; CLARK, J. P., LANGFORD, V. M. & WILKINS,C. J., J. chem.Soc.,A (1967). 792; KUMAR DAS, V. G. &'KITCHING, W., I organometal.Chem.,13 (1968), 523.11. Il'AuL, R C., MADAN, H. & CHADHA, S. L., J. inorg.nucl.i Chem.,36 (1974),737; 37 (1975),447.12. Il'AUL, R C., SINGH, P., MAKHNI, H. S. & CHADHA, S. L.,iI inorg.nucl. Chem.,32 (1970), 2141.13. :fAWASKI, Y., TANAKA, T. & OKAWARA, R., I organo-1metal.Chem.,6 (1966), 95.14. 1'AUL, R C., SINGH, H. & CHADHA, S. L., Indian I Chem.,,15A (1977), 121.15. I1'AUL,R C. & CHADHA, S. L., unpublished work.16. ljlEATTIE, I. R, McQUILLaN, G. P., RULE, L. & WEBSTER,M., I chem.Soc., (1963), 1514.17. CLARK, R J. H. & ERRINGTON, W., I chem.Soc., A(1967), 258.654Complexes of DibutyItin(IV) with2-AminobEnzoic Acids & 2-(Monotertiary-arsino)benzoic AcidsS. S. SANDHU, J. K. SINDHU & G. K. SANDHUDepartment of Chemistry, Guru Nanak Dev UniversityAmritsarReceived2 February 1976; revised21 July 1976accepted3 February 1977Complexesof di(n-butyl)tin(IV) havebeenpreparedwith (a) 2-aminobenzoicacid, (b) N-methyl-2-amino-benzoic acid, (c) 2-amino-5-chlorobenzoic acid,(d) N-phenyl-2-aminobenzoicacid, (e) 2-(diphenyl-arsino)benzoicacid and (f) 2-{di(p-tolyl)arsino}benzoicacid. On the basis of analyticaldatathesecomplexeshavebeenassignedthreetypesof formulae,(i) (C,H')2-SnL" (ii) (C,H,)2Sn(L'2)L'Hand (Hi) (CjHg)2(L")SnhO,whereLH is (a), (c), (d), (f), L'H is (b) and L"H is (e).Complexesof the type (i) and (iii) are monomeric.The infrared data indicate the absenceof bondingbetweennitrogen or arsenic of these ligands andtin(IV). However, bidentate nature of carboxylategroupoftheseligandshasbeenestablishedon thebasisof IR spectra. Hexa-coordinatedstructureshavebeensuggestedfor all thecomplexesexcept{(C4Hg)2(L")Sn},0which is penta-coordinated.pREPARATION and characterizationof com-plexesof 2-amino-,N-methyl-2-amino-,2-ami'lo-5-clloro-,N-phenyl-2-amino-,2-(diphenylarsirlo)-and2-{di(P-tolyl)arsino}-benzoicacids with dibutyltintIV) oxide are reportedin tbis paper. A penta-coordinatedtin(IV) complexwith 2-aminobenzoicacidhas beenreportedl.2-Amino-,N-methyl-2-amino-,N-phenyl-2-amino-benzoicacidswereavailablecommerciallyandusedafter purificat;oll 2-Amino-5-chlorobenzoicarid2,2-(diphenylarsino)bellzoicacid a:ld 2-{di(P-tolyl)-arsino}benzoicacicP were prepared by k;lOwnmethods. Estersof aminobenzoirand substitutedamillobenzoicarids were preparedas describedeilrlier4. Di(n-butyl)tiil(lV) oxide wa<'procuredfrom M/s AHa Inorga:lics.The complexeswere preparedby refl.uxinganequimolarmixture of the liga'ld (0,1 mole)anddibutyltinoxide(0·1mole)in a 1:1mixtulc of drybenzeneandabsoluteethylalcohol(30ml) for 4 hr.DeanandStarkseparatorwasusedto removewaterfrom the reaction mixture. After removingthesolvent the solid product was crystallizedfromdry pet. ether(60-80°)and dried in vacuo.ElementalanalysiswasobtainedfromAustralianMicroanalyticalService. Tin was estimatedastin dioxide. ::\Iolecularweights were determinedin benzeneby cryoscopicmethod. The IR spectrawererecordedin nuj01 in therange4000-650cm-Ion a Carl Zeiss Specord 71 instrument. NMRspectra were recordedOn Tesla BS 487 NMRspectrometer(80MHz).Analyticalre:;ultsCfable1) indicatethreetypesof stoichiometri(~s:(i) (C4H9hSnL2, (ii) (C4H9hSn(L~)(L'H) a:ld (iii) {(C4H9)2(L")SnhO (whereLHis 2-aminobenzoica id,2-amino-5-chlorobenzoicacid,I1II

Complexes of Triphenylarsine Oxide with Trichlorotin(IV) & Trichlorotitanium(IV) Alkoxides & Dichlorotitanium(IV) Dialkoxides

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Complexes of Triphenylarsine Oxide with Trichlorotin(IV) & Trichlorotitanium(IV) Alkoxides & Dichlorotitanium(IV) Dialkoxides

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