Reactivity of Amido Ligands on a Dinuclear Ru(II) Center: Formation of Imido Complexes and C−N Coupling Reaction with Alkyne

Treatment of a dinuclear Ru(II) amido complex [Cp*Ru(μ2-NHPh)]2 (Cp* = η5-C5Me5) with small organic substrates including CO, tert-butyl isocyanide, a sulfur ylide Ph2SCH2, and diphenylacetylene resulted in an unexpected disproportionation reaction of the bridging amido ligands to produce a free amine and a series of imido-bridged diruthenium complexes [(Cp*Ru)2(μ2-L)(μ2-NPh)] (L = CO, t-BuNC, CH2). In the case of diphenylacetylene, the bridging imido ligand underwent subsequent coupling reaction with the coordinated alkyne to form an iminoalkenyl complex [(Cp*Ru)2(μ2-PhNCPhCPh)].

将双核钌(II)氨基配合物[Cp*Ru(μ₂-NHPh)]₂（其中Cp*代表η⁵-五甲基环戊二烯基，即η⁵-C₅Me₅）与一氧化碳（carbon monoxide）、叔丁基异氰（tert-butyl isocyanide）、硫叶立德（sulfur ylide）Ph₂S=CH₂以及二苯基乙炔（diphenylacetylene）等小分子有机底物进行反应时，桥联氨基配体发生意外歧化反应，生成游离胺与一系列亚胺基桥联双核钌配合物[(Cp*Ru)₂(μ₂-L)(μ₂-NPh)]（L = CO、t-BuNC、CH₂）。在二苯基乙炔的反应体系中，桥联亚胺基配体还会与配位炔烃发生后续偶联反应，最终得到亚氨基烯基配合物[(Cp*Ru)₂(μ₂-PhNCPhCPh)]。