Reactivity of vinylidene complexes of ruthenium with hydrazines and hydroxylamines.

Vinylidene complexes [Ru(η(5)-C5H5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)R}(PPh3)L]BPh4 (, ) [L = P(OMe)3, P(OEt)3; R = Ph, p-tolyl, Bu(t), H] react with hydrazine R1NHNH2 (R1 = H, Me, Ph) to afford nitrile derivatives [Ru(η(5)-C5H5)(N[triple bond, length as m-dash]CCH2R)(PPh3)L]BPh4 (, ) and amine R1NH2. Hydroxylamine NH2OH also reacts with vinylidenes , to yield nitrile derivatives , and H2O. Studies with (15)N-labeled hydrazine and DFT calculations allowed a reaction path to be proposed. The complexes were characterized by spectroscopy (IR, (1)H, (31)P, (13)C and (15)N NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5H5)(N[triple bond, length as m-dash]CCH2Ph)(PPh3){P(OEt)3}]BPh4 ().