The reaction of TiCl 4 with pyridine- and pyrimidine-thiol has been investigated. Reaction of TiCl 4 with 3 equiv. of 2-mercaptopyridine and 3 equiv. of tert-butylpyridine in toluene at room temperature resulted in the formation of the tris(pyridine-2-thiolate) complex [TiCl(SC 5H 4N) 3] ( 1). The related reaction between TiCl 4 with 3 equiv. of 2-mercaptopyrimidine and 3 equiv. of tert-butylpyridine in toluene at room temperature resulted in the isolation of the complex [TiCl(SC 4H 3N 2) 3] ( 2). Compound 2 has been characterised by X-ray crystallography. Low pressure CVD of 1 and 2 produced brown/gold films of TiS 2/TiO 2 on glass substrates at 550 and 600 °C.