Facile S−S Bond Activation of Alkyl and Aryl Disulfides by [RuCp(CH<sub>3</sub>CN)<sub>3</sub>]<sup>+</sup>: Formation of Dinuclear Ru(III)−Ru(III) Complexes with Bridging Thiolate Ligands<sup>†</sup>
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We describe a way to enter into dinuclear RuCp thiolate chemistry, since hitherto only the RuCp* derivatives have been available. When the labile cationic complex [RuCp(CH3CN)3]+ is reacted with alkyl or aryl disulfides RSSR (and likewise PhSeSePh), oxidative addition takes place. As a result, dinuclear Ru(III)−Ru(III) complexes of the type [CpRu(CH3CN)(μ-SR)2(CH3CN)RuCp](PF6)2 are formed, featuring a metal−metal single bond and bridging thiolate ligands. The reaction of [RuCp(CH3CN)3]+ with bis(2-pyridyl) disulfide affords, depending on the reaction conditions, either the dinuclear complex [CpRu(μ-pyS)2RuCp](PF6)2 or the mononuclear complex [CpRu(κ2N,S-pyS)2]PF6. The substitutionally labile acetonitrile ligands in [CpRu(CH3CN)(μ-SR)2(CH3CN)RuCp](PF6)2 are readily replaced by other donor ligands. For instance, treatment of [CpRu(CH3CN)(μ-S-t-Bu)2(CH3CN)RuCp](PF6)2 with KBr affords the neutral complex CpRuBr(μ-S-t-Bu)2BrRuCp, while with t-BuSH the dinuclear complex sym-[CpRu(μ-S-t-Bu)3RuCp]PF6 containing three bridging thiolate ligands is formed. Representative X-ray structures are presented.
