P−H Bond Addition to a Dinuclear Ruthenium Imido Complex: Synthesis and Reactivity of an Amido Phosphido Complex

Treatment of the imido complex [(Cp*Ru)2(μ2-NPh)(μ2-CO)] (3; Cp* = η5-C5Me5) with phenylphosphine resulted in the P−H bond addition across the Ru−N bonds to give the amido phosphido complex [(Cp*Ru)2(μ2-NHPh)(μ2-PHPh)(μ2-CO)] (4). Exposure of 4 to atmospheric carbon monoxide resulted in the formation of the phosphinidene complex [{Cp*Ru(CO)}2(μ2-PPh)(μ2-CO)] (6) and aniline. With excess phenylphosphine, compound 4 gave the bis(phosphido) phosphine complex [Cp*Ru(CO)(μ2-PHPh)2Ru(PH2Ph)Cp*] (5). Treatment of 4 with 2-propanol led to an overall hydrogenolysis of the Ru−N bonds to give the hydrido phosphido complex [(Cp*Ru)2(μ2-H)(μ2-PHPh)(μ2-CO)] (7). Reaction of 4 with 4-tert-butylphenol resulted in a P−O bond formation yielding the hydrido aryloxyphosphido complex [(Cp*Ru)2(μ2-H)(μ2-PPh(OC6H4-t-Bu-p)(μ2-CO)] (8). Crystal structures of 4, 5, and 8 are reported.