Titanium(IV) Chloro-Derivatives of Strong Monobasic Acids

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Abstract
The interaction of the monobasic protonic acids HSO3F, HSO3CH3, HPO2F2, and HCO2CF3 with titanium(IV) 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 TiCl2Y2, with Y = oxyacid group, are formed, the excess of TiCl4 results in the formation of TiCl3.33(SO3F)0.66, TiCl3SO3CH3, and again TiCl2(PO2F2)2 and TiCl2(CO2CF3)2.The first two compounds are also obtained by ligand redistribution reactions with TiCl4 in excess, e.g.[Formula: see text]in quantitative yield.Vibrational spectra for the PO2F2, SO3F and the previously reported SO3CF3 derivatives are interpreted in terms of hexacoordinated titanium and generally bi- or tridentate oxyacid groups. In TiCl3.33(SO3F)0.66 evidence for a highly unusual tetradentate SO3F group is presented, where coordination to titanium involves all three oxygens as well as fluorine.

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