Synthesis and structures of two isomeric pairs of tetrathiotungstate clusters, [{Cp*Ru(CO)}2(WS4){W(CO)4}] and [{Cp*Ru(CO)}2(WS4)] (Cp* = η5-C5Me5), by reaction of [Cp*2Ru2S4] with [W(CO)3(NCMe)3]

An isomeric pair of tetranuclear clusters containing tetrathiotungstate [WS4](2-), [{Cp*Ru-(CO)}(2){W(mu(3)-S)(2)(mu(2-)S)(2)}{W(CO)(4)}] (1a) and [{Cp*Ru(CO)}(2)(W(mu(3)-S)(3)(=S)}{W(CO)(4))] (2a) (Cp* = eta(5)-C5Me5), and the trinuclear cluster [{Cp*Ru(CO)}(2){W(mu(3)-S)(mu(2)-S)(2)(=S)}] (3a) were formed upon thermal reaction of [Cp*2Ru2S4] with 2 equiv of [W(CO)(3)(NCMe)(3)]. In the course of the reaction, redistribution of CO and S ligands took place between Ru and W atoms without losing any CO and S ligands. When the reaction was performed with 1 equiv of [W(CO)(3)(NCMe)(3)], 2a and the trinuclear cluster [{Cp*Ru(CO)}(2){W(mu(2)-S)(4)}] (5a), vclhich is the isomer of 3a, were obtained. Trinuclear clusters 3a and 5a were converted to tetranucIear clusters la and 2a by the reaction with [W(CO)(3)(NCMe)(3)] and CO. Thus, the trinuclear clusters 3a and 5a were considered to be intermediates to give the tetranuclear clusters 1a and 2a.