ADDUCTS OF TITANIUM TETRACHLORIDE WITH ORGANOSULFUR COMPOUNDS - CRYSTAL AND MOLECULAR-STRUCTURES OF TICL4(C4H8S)(2) AND (TICL4)(2)(CH3SSCH3)

Treatment of titanium tetrachloride with a range of organothiols affor ds adducts of the formula TICl4(HSR)(2) in 77-89% yields. Reaction of titanium tetrachloride with organic sulfides gives sulfide adducts of the formula TiCl4(SR2)(2) in 87-98% yields. These complexes are volati le and monomeric with cis-organosulfur ligands. Treatment of titanium tetrachloride with methyl disulfide affords the adduct (TiCl4)(2)(CH3S SCH3) in 98% yield, which adopts a dinuclear structure with a Tl2Cl8 c ore and a bridging disulfide ligand. The crystal structures of TICl4(C 4H8S)(2) and (TiCl4)(2)(CH3SSCH3) were determined. The relevance of th ese observations to the chemical vapor deposition of titanium disulfid e and trisulfide films is discussed. (C) 1997 Elsevier Science Ltd.