Adducts of titanium tetrachloride with organosulfur compounds. Crystal and molecular structures of TiCl 4(C 4H 8S) 2 and (TiCl 4) 2(CH 3SSCH 3)

Abstract

Treatment of titanium tetrachloride with a range of organothiols affords adducts of the formula TiCl 4(HSR) 2 in 77–89% yields. Reaction of titanium tetrachloride with organic sulfides gives sulfide adducts of the formula TiCl 4(SR 2) 2 in 87–98% yields. These complexes are volatile and monomeric with cis-organosulfur ligands. Treatment of titanium tetrachloride with methyl disulfide affords the adduct (TiCl 4) 2(CH 3SSCH 3) in 98% yield, which adopts a dinuclear structure with a Ti 2Cl 8 core and a bridging disulfide ligand. The crystal structures of TiCl 4(C 4H 8S) 2 and (TiCl 4) 2(CH 3SSCH 3) were determined. The relevance of these observations to the chemical vapor deposition of titanium disulfide and trisulfide films is discussed.