Thiolate derivatives of titanium(iv) and tantalum(v) as precursors to metal sulfides

Reaction of Ta(NMe2)5 with 10 equivalents of 2,6-Me2C6H3SH in toluene resulted in the formation of bright red crystals of [Ta(SC6H3Me2-2,6)4(NMe2)] (1). The related reaction between Ti(NEt2)4 and 10 equivalents of ButSH in toluene afforded a mixture of two complexes, [Ti(SBut)4] (3) and [Ti(SBut)3(NEt2)] (4). X-Ray crystal structures of 1 and 4 have been determined. Vapour phase thin-film studies of compounds 1 and 3/4 revealed that 1 is not an effective tantalum sulfide precursor whereas 3/4 produced TiS2.