The reaction of TiCl4 with hexamethyldisilathiane in diethyl ether at room temperature affords black precipitates which upon annealing under H2S at 800 degreesC results in the formation of crystalline TiS2. Similarly, reaction Of MCl5 (M = Nb, Ta, Mo) with S(SiMe3)(2) in diethyl ether at room temperature or toluene at reflux results in the initial formation of black precipitates MxSyClzSipCqHp. Annealing of these precipitates under static vacuum at 550 or at 800 degreesC under H2S affords MS2. The black precipitates and metal sulfides produced under all annealing conditions were analysed by powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy. (C) 2003 Elsevier Science Ltd. All rights reserved.