Preparation of a Heterobimetallic Cluster with Bridging Sulfido and Thiolato Ligands [{(η5-C5Me5)Ru}{(η5-C5Me5)Ir}2(μ3-S)(μ2-SCH2CH2CN)2Cl] and Its Transformations into Alkyne, CO, Isocyanide, and Iminoacyl Clusters

Abstract

A diiridium complex containing bridging sulfido and thiolato ligands [Cp*Ir(μ-S)(μ-SCH2CH2CN)2IrCp*] (Cp* = η5-C5Me5) reacted with [(Cp*Ru)4(μ3-Cl)4] in THF at room temperature to afford the trinuclear sulfido-thiolato cluster [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)2Cl] (4). Treatment of 4 with HC⋮CCOOMe, CO, and 2,6-Me2C6H3NC (XyNC) at room temperature in the presence of KPF6 resulted in the incorporation of these molecules into the Ir2 or Ir site of this cluster core, yielding [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)2(μ2-HCCCOOMe)][PF6] (5) and [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)2(L)][PF6] (L = CO (7), XyNC). On the other hand, 4 reacted with excess KPF6 along with 1 equiv of 2,6-dimethylpyridinium chloride to give [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)(μ3-SCH2CH2CNH)][PF6]2 (9‘), which presumably formed through the binding of the CN group in one cyanoethylthiolato ligand to the Ir2 site, followed by the protonation of its N atom. Single-crystal X-ray analyses were undertaken to determine the detailed structure...