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 [WS 4 ] 2 -, [{Cp*Ru(CO)} 2 {W(μ 3 -S) 2 (μ 2 -S) 2 }{W(CO) 4 }] ( 1a ) and [{Cp*Ru(CO)} 2 {W(μ 3 -S) 3 ( S)}{W(CO) 4 }] ( 2a ) (Cp* = η 5 -C 5 Me 5 ), and the trinuclear cluster [{Cp*Ru(CO)} 2 {W(μ 3 -S)(μ 2 -S) 2 ( S)}] ( 3a ) were formed upon thermal reaction of [Cp* 2 Ru 2 S 4 ] 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(μ 2 -S) 4 }] ( 5a ), which is the isomer of 3a, were obtained. Trinuclear clusters 3a and 5a were converted to tetranuclear clusters 1a 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 .