Reactions of (PCP)Ru(CO)(NHPh)(PMe₃) (PCP = 2,6-(CH₂P^tBu₂)₂C₆H₃) with Substrates That Possess Polar Bonds

The Ru(II) amido complex (PCP)Ru(CO)(PMe₃)(NHPh) (1) (PCP = 2,6-(CH₂P^tBu₂)₂C₆H₃) reacts with compounds that possess polar CN, C⋮N, or CO bonds (e.g., nitriles, carbodiimides, or isocyanates) to produce four-membered heterometallacycles that result from nucleophilic addition of the amido nitrogen to an unsaturated carbon of the organic substrate. Based on studies of the reaction of complex 1 with acetonitrile, the transformations are suggested to proceed by dissociation of trimethylphosphine, followed by coordination of the organic substrate and then intramolecular N−C bond formation. In the presence of ROH (R = H or Me), the fluorinated amidinate complex (PCP)Ru(CO)(N(Ph)C(C₆F₅)NH) (6) reacts with excess pentafluorobenzonitrile to produce (PCP)Ru(CO)(F)(N(H)C(C₆F₅)NHPh) (7). The reaction with MeOH also produces o-MeOC₆F₄CN (>90%) and p-MeOC₆F₄CN (<10%). Details of the solid-state structures of (PCP)Ru(CO)(F)(N(H)C(C₆F₅)NHPh) (7), (PCP)Ru(CO)[PhNC{NH(hx)}N(hx)] (8), (PCP)Ru(CO){N(Ph)C(NHPh)O} (9), and (PCP)Ru(CO){OC(Ph)N(Ph)} (10) are reported.