Reactivity of tetrakisdimethylamido-titanium(iv) and -zirconium(iv) with thiols

The reaction of [M(NMe2)4] (M = Ti, Zr) with thiols has been investigated. Reaction of [Ti(NMe2)4] with an excess of CF3CH2SH in hexanes at room temperature resulted in the formation of the ionic complex [Me2NH2]2[Ti(SCH2CF3)6] (1). The related reaction between [Zr(NMe2)4] and 4 equivalents of ButSH at room temperature resulted in the isolation of the ionic complex [Me2NH2][Zr2(μ-SBut)3(SBut)6] (2). In contrast, reaction of [Zr(NMe2)4] and 4 equivalents of 2-mercaptopyridine (HSC5H4N) afforded the neutral complex [Zr(SC5H4N)4] (3). Compounds 1 and 2 have been characterised by X-ray crystallography. Low pressure CVD of [Me2NH2]2[Ti(SCH2CF3)6] produced purple films of TiS2 on glass substrates at 550 °C.