Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex

The hydrosulfido-bridged diruthenium complex [Cp*RuCl(μ2-SH)2RuClCp*] (1) reacted with an excess of triethylamine to give the cubane-type tetraruthenium sulfido cluster [(Cp*Ru)43-S)4] (3). When the reaction was carried out in the presence of alkynes, the dithiolene-bridged diruthenium complexes [(Cp*Ru)2224-S2C2RR‘)] (4) were obtained. The dithiolene ring in 4 is almost planar. Treatment of 4 with CO afforded the carbonyl complexes [Cp*Ru(CO)(μ224-S2C2RR‘)RuCp*] (5) containing a bent dithiolene ring. On the other hand, the reaction of 1 with an equimolar amount of [RuH2(PPh3)4] resulted in the formation of the triruthenium sulfido cluster [(Cp*Ru)23-S)22-H)RuCl(PPh3)2] (6). Cluster 6 reacted with an excess of NaBH4 in ethanol to give the dihydrido cluster [(Cp*Ru)23-S)22-H)RuH(PPh3)2] (7), which was further converted to the dicarbonyl cluster [(Cp*Ru)23-S)2Ru(CO)2(PPh3)] (8) under CO. The detailed structures for [(Cp*Ru)2224-S2C2HBut)] (4a), [Cp*Ru(CO)(μ224-S2C2HBut)RuCp*] (5a), and 68 have been determined by X-ray crystallography.