Parashar, G. K.

Rai, A. K.

Tripathi, U. D.

English

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INDIAN J. CHEM., VOL. 14A, MARCH 19766. CLARK, R. J. H. & WILLIAMS, C. S., Inorg. Chem., 4(1965), 350.7. FIGGIS, B. N., Introduction to ligand fields (Interscience,New York), 1966.8. DUFF, E:.J/.)HUGH~S, M. N. & ~UTT,I~. J.,J.chem.Soc.(A), (1%8),2354, (1969), ~-'i', 2M6, 2101.9. LEVER, A. B. P., Inorganic electronic spectroscopy (Else-vier, London), (1966), 355.10. ITOH, K. & BERNSTEIN, H. J., Can. J. Chem., 34 (1956),170.11. ADAMS, D. M., Metal-ligand and related uibraiions (Aro-nold, London), 1967, 362.Oxy-Ti(IV) DicarboxylatesG. K. PARASHAR,U. D. TRIPATHI & A. K. RAIDepartment of Chemistry, University of Rajasthar , JaipurReceived 16 January 1975; accepted 8 April 1975Oxy-titanium(IV) carboxylates of compositionTiO(OOCR). ha-vebeen synthesized by controlled hydro-lysis of dialkoxy titanium dicarboxylates. These areobtained as viscous liquids, semisolids or solids,depending upon the chain length of carboxylic acids.Their refractive indices, melting points, molecularweights, thermal decomposition and IR data arereported.TIT ANYL compo~mds possess diffe.rent types ofmetal-oxygen linkages>" depending upon theroutes of their synthesis and molecular association.Some of these derivatives find extensive industrialapplications+ The possibility of the formation ofoxycarboxylates has been indicated by Mehrotraand Pandey" during their attempts to synthesizetitanium tetra soaps. In the present note we reportthe synthesis of some oxy-titanium dicarboxylates.Their refractive indices, melting points, molecularweights, IR spectra and thermal decomposition dataare also being reported.Oxy-titanium dicarboxylates were synthesized bycontrolled hydrolysis of dialkoxy-titaniurn dicar-boxylates in benzene solution (Eq. 1).refluxTi(OPri)2(OOCR)2+HOH ------+ TiO(OOCR)2+2PriOH t ...(1)PriOR produced in the reaction was removedazeotropically using benzene and estimated quanti-tatively. The excess solvent was distilled out underreduced pressure and the products obtained werefinally dried at 50%.5 mm.The products are viscous liquids. semisolids orsolids depending upon the number of carbon atomsin the carboxylic acid chain. The liquid derivativeshave very little difference in their refractive indices(Table 1).The ebullioscopic and osmometric molecular weightdeterminations in benzene solution show little ten-dency of association. The molecular complexitiesfall in the range 1·2-1·4. The plot of the weight ofcompound added to a measured quantity of benzeneagainst the change in resistance is always linearshowing that the molecular complexity is indepen-dent of concentration of the solute within themeasured range.The IR spectra of TiO(OOCRh derivatives (innujol or neat) show the presence of two types ofTABLE 1 - ANALYTICALAND PHYSICOCHEMICALDATA OF OXY-TITANIUMCARBOXYLATESReactants Isopropanol Product Yield (g) Ti (%) Mol. wt.(g) (g) Found Found Found Found(calc.) (calc.) (calc.) (calc.)Ti(OPri)2(OOCC7H15)2 (2-10) 0'24 TiO(OOCC7H1S); 1·70 13'52 451H20 (0'10) (0'28) .~!5 = 1.4975 (t '63) (13-68) (350)*Ti(OPri)2(OOCCllH23)2 (3'36) 0·30 TiO(OOCCllH..)2 2'82 10·05 592H20 (0'11) (0'33) 'I)~5= 1.4902 (2'73) (10'35) (462)Ti(OPri)2(OOCC13H27)2 (1'36) 0'10 TiO(OOCC13Hd; 1'23 9·02 662H20 (0'04) (0·13) 'I);; = 1'4882 (1'14) (9'23) (519)Ti(OPri).(OOCClSH31)' (4'21) 0·36 TiO(OOCC15H31)~ 3'69 8'23 733H20 (0'20) (0'37) (3-58) (8'34) (575)Ti(OPri)2(OOCC17H33)2 (5'51) 0'43 TiO(OOCC17H3,); 4·72 7'78 751H20 (0'14) (0'45) 'I)~5= 1'4978 (4'74) (7'65) (626)DTi(OPri)2(OOCC17H35)2 (4-41) 0·33 TiO(OOCC17H3S)t 3'85 7'50 857H20 (0'12) (0'36) (rn.p. 58-9°) (3'79) (7'59) (630)(886)§Ti (0Pri) 2(OOCC21H..) 2 (3'04) 0'21 TiO(OOCC21H43)~ 2'81 6'38 908H20 (0'07) (0'22) (m.p, 65-6°) (2-68) (6'45) (743)(1038)§*Viscous liquid.+Semisolid.tWhite solid.§Molecular weight determined by osmometry.208L,carboxylate groups. A band at .--.1730 cm-1 whichhas been assigned to 'JC=O in metal carboxylatess-",where carboxylic acid behaves as a unidentate ligand,was found to be present in all these derivatives.Two other bands present at .--.1560 and .--.1450 crrr+may be assigned to 'JaCOO- and 'JsCOO-respectively.These indicate the bidentate" nature of carboxylategroups.No bands are observed in the regions .--.3500,.--.1130 and 1100-900 cm-1 corresponding to hydroxy,isopropoxy and Ti=O stretching'<" respectively,indicating the absence of any free acid orTi(OPri)2(00CR)2 species. However, a broad bandaround 835 crrr+ observed in these derivatives maybe assigned to Ti=O.-,..Ti type of linkage-s. As themolecular weight data are not in agreement withpolymeric or dimeric structures, it may be suggestedthat the coordination between terminal oxygen andtitanium atoms is destroyed in solution giving riseto monomeric species and consequently the mole-cular weight falls corresponding 10 the molecularcomplexity 1·3.These derivatives have no tendency of adductformation with nitrogen containing ligands likepyridine.The compounds are thermally stable up to 200°above which temperature these decompose slowly,giving CO, CO2, H20 and leaving Ti02 as theresidue, About 80% of its decomposition is com-pleted around 300°.This mode of decomposition of TiO(00CR)2 deri-vatives is different from that of other metal carboxy-lates13,14 in which the decomposition proceeds withthe formation of a ketone as an intermediateproduct.The authors thank Prof. K. C. Joshi, Head of theDepartment of Chemistry, University of Rajasthan,Jaipur, for providing laboratory facilities and theCSIR, New Delhi, for the award of a JRF toG. K. P.References, 1. DEHNICKE, K., Chem se«, 98 (1965), 29l.2. COLLIS, R. E., J. chem. Soc. (A), (1~), 1895.3. SELBIN, J., J. chem, Educ., 41 (1964),87.4. HARWOOD, J. H., Industrial applications of organo-metallic compounds (Chapman & Hall, London),1962.5. PANDEY, K. C. & MEHROTRA, R. C., J. prakl. Chem., 5(1967), 10l.6. PIKE, R. M. & LUONGO, R. R., J. Am. chem, Soc., 87(1965), 1403.7. PIKE, R. M. & LUONGO, R. R., J. Am. chem. Soc., 88(1966), 2972.8. STEPHENSON, T A., MOREHOUSE, S. M., POWELL, A. R.,HEFFER, J. P. & WILKINSON, G., J. chem. Soc. (A),(1965), 3632.9. Cox, M., LEWIS, J. & NYHOLM, R. S., J. chem, Soc., (1965),2840.10. FOWLES, G. W. A., _LEWIS, D. F. & WALTON, R. A., J.chem. Soc. (A), (1968), 1468.11. BARRACLOUGH, C. G., LEWIS, J. & NYHOLM ,R. S., J.chem. Soc., (1959), 3552.12. KALINNIKOV, V. T, ZELENTSOV, V. V., VOLKOV, M. N.& SHOSTAKOVSKII, S. M., Chem, ,.Abslr., 62 (1965),9941 C. ~13. MISRA, S. N., MISRA, T N. & MEHROTRA, R. C., J. inorg.nucl. Chem., 25 (1963), 195.14. RAI, A. K. & MEHROTRA, R. C., J. Indian chem. Soc., 40(1963), 359.NOTESPenta coordinated Ti(IV) Chloride &Sn(IV) Bromide & Iodide Complexes withAcridine & PiperazineS. A. A. ZAIDI, K. S. SIDDIQI & (Mrs) N. S. NEELAMDepartment of Chemistry, Aligarh Muslim UniversityAligarh 202001Received 24 December 1974; accepted 31 March 1975Donor-acceptor type complexes of TiCI., Sn'Br; andSnf., with acridine and piperazine have been preparedand characterized on the basis of conductance and IRdata. A pentacoordinated trigonal bipyramidal struc-ture has been proposed for all the complexes. The(TiCI')2-piperazine complex has been found to bebinuclear.IN continuation of our earlier work+" on the com-plexes of acridine and piperazine with SnCl4 andGeCI4, the preparation and characterization of TiCI4,SnBr4 and SnI4 complexes with these donor mole-cules are reported in this note. The possibility ofthe formation of a binuclear complex with pipera-zine has also been considered. Molecular additioncompounds of group (IV) halides have extensivelybeen studied+".Acridine (Fluka AG, m.p. 108°) was recrystallizedfrom alcohol. Piperazine hexahydrate (E. Merck, m.p.56°) was used as such without further purification.Anhydrous Ti(IV) chloride (BDH) was used whereasSn(IV) bromide and iodide were prepared accordingto standard methods".Acridine complexes - A solution of Sn(IV) bro-mide/iodide in ethanol-chloroform mixture was addedto an ethanolic solution of acridine in approxi-mately equimolar quantity. Sn(IV) bromide yieldeda greenish yellow crystalline substance but Sn(IV)iodide gave a gelatinous mass which dissolved onstirring. However, this solution later yielded ayellowish orange compound. Ethanolic solutions ofTi(IV) chloride and excess of acridine when leftovernight after mixing yielded needle-shaped crys-tals. All the solids obtained were washed withethanol and dried in vacuo.Piperazine complexes - These were also preparedas above but the complex formation was rapid inthe case of Sn(IV) iodide and Ti(IV) chloride where-as with Sn(IV) bromide a granular product wasobtained after a few minutes.The melting points and analyses of the complexesare given in Table 1. All the addition compoundsformed with acridine and piperazine are of the typeMX4: L, except the adduct of TiCl4 with piperazinewhich is of (MX4)2: L type.The molar conductances (Systronix conductivitybridge) of approximately 10-3 millimolar solutionsof the adducts of acridine in nitromethane at roomtemperature fall well below the range for a uni-univalent electrolyte'", indicative of non-ionic natureof these adducts.Acridine exhibits two strong bands in its IRspectrum at 1515 and 1555 crrr ' attributable to'JC=C and 'JC=N respectively. Its adducts withTiCI4, SnBr4 and SnI4 exhibit 'JC=C and 'JC=N209

Oxy-Ti(IV) Dicarboxylates

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Oxy-Ti(IV) Dicarboxylates

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