| Abstract
| - The trinuclear sulfido-thiolato cluster [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)2Cl] (Cp* = η5-C5Me5) was obtained by treatment of the diiridium μ-thiolato complex [Cp*Ir(μ-S)(μ-SCH2CH2CN)2IrCp*] with [(Cp*Ru)4(μ3-Cl)4], which was further converted into new alkyne, CO, isocyanide, and iminoacyl clusters.
- 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 temperatureto 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 Ir2or 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-dimethylpyridiniumchloride to give [(Cp*Ru)(Cp*Ir)2(μ3-S)(μ2-SCH2CH2CN)(μ3-SCH2CH2CNH)][PF6]2 (9‘), whichpresumably formed through the binding of the CN group in one cyanoethylthiolato ligandto the Ir2 site, followed by the protonation of its N atom. Single-crystal X-ray analyses wereundertaken to determine the detailed structures for 4, 5, 7, and 9‘.
|
