The interaction of the monobasic protonic acids H S 0 3 F , HS03CH3, H P 0 2 F 2 , and HCOzCF3 with titanium(1V) chloride at room temperature is studied with either the acid or the metal halide in excess. Whereas with the acid in excess products of the type TiCI2Y2, with Y = oxyacid group, are formed, the excess of TiCI, results in the formation of TiC13.33(S03F)o.66, TiC13S03CH3, and again TiC12(P02F2)2 and TiC12(C02CF3),.The first two compounds are also obtained by ligand redistribution reactions with TiCI, in excess, e.g.in quantitative yield. Vibrational spectra for the P02F2, S 0 3 F and the previously reported S 0 3 C F 3 derivatives are interpreted in terms of hexacoordinated titanium and generally bi-or tridentate oxyacid groups. In TiC13.33(S03F)o.66 evidence for a highly unusual tetradentate S 0 3 F group is presented, where coordination to titanium involves all three oxygens as well as fluorine.L'interaction des acides protoniques monobasiques, H S 0 3 F , HS03CH3, H P 0 2 F 2 et H C 0 2 C F 3 avec le chlorure de titane(1V) a t t t etudite a temptrature ambiante en employant soit I'acide, soit I'halogtnure mttallique en excts.Lorsque l'acide est en excts, on note la formation de produits du type TiC12Y2 ou Y = groupe oxyacide; par contre, I'exces de TiCI, conduit a la formation de TiC13.33(S03F)0.66, de TiCI3SO3CH3, deLes deux premiers composts sont aussi obtenus quantitativement a I'aide de reactions de redistribution du coordinat en prtsence d'un excis de TiCI,, e.g. 25 "C TiC12(S03CH3)2 + TiCI4 + 2TiC13S03CH3Les spectres de vibration des dtrivts P02F2-, S03F-et S03CF3-, lequel a dtja ett rapportt. sont interprttts en fonction de titanium hexacoordonne et de groupes oxyacides gtneralement bi ou tricoordonnts. Dans le TiC13.33(S03F)o.66, on met en tvidence la prtsence d'un groupe S 0 3 F tetracoordonnt assez inhabituel oh la coordination du titanium implique les trois oxygenes ainsi q u e le fluor.[Traduit par le journal]Can. J. Chern., 52, 231 (1974)
Die Solvolyse von TiCl4 bei Raumtemperatur durch die Säuren HSO3F, HSO3CH3, HPO2F2 und HCO2CF3 wird untersucht, wobei einmal TiCl4 und einmal die.
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