Synthesis and Structures of 1,1‘-Ferrocenedithiolato-Bridged Di- and Trinuclear Ruthenium Complexes

The 1,1‘-ferrocenedithiolato-bridged (arene)ruthenium(I) complex [{(p-cymene)Ru}2(μ2-S2fc)] (4; p-cymene = 4-isopropyltoluene, S2fc = 1,1‘-ferrocenedithiolato) was synthesized by the reaction of 1,1‘-ferrocenedithiol (1) with [(p-cymene)RuCl2]2 (2) and subsequent reduction with sodium amalgam; reactions of 4 with HOTf and MeOTf (OTf = OSO2CF3) afforded the hydrido complex [{(p-cymene)Ru}2(μ2-H)(μ2-S2fc)][OTf] (5) and the thiolato−thioether complex [{(p-cymene)Ru}2(μ2-SfcSMe)][OTf] (6), respectively. On the other hand, treatment of [Cp*RuCl]4 (7; Cp* = η5-C5Me5) with 1,2,3-trithia[3]ferrocenophane (8) resulted in the formation of the (1,1‘-ferrocenedithiolato)(sulfido)triruthenium cluster [(Cp*Ru)3(μ3-S)(μ3-S2fc)(μ2-Cl)][FeCl4] (9).