Reactivity of vinylidene complexes of ruthenium with hydrazines and hydroxylamines†
Abstract
Vinylidene complexes [Ru(η5-C5H5){CC(H)R}(PPh3)L]BPh4 (1, 2) [L = P(OMe)3, P(OEt)3; R = Ph, p-tolyl, But, H] react with hydrazine R1NHNH2 (R1 = H, Me, Ph) to afford nitrile derivatives [Ru(η5-C5H5)(NCCH2R)(PPh3)L]BPh4 (3, 4) and amine R1NH2. Hydroxylamine NH2OH also reacts with vinylidenes 1, 2 to yield nitrile derivatives 3, 4 and H2O. Studies with 15N-labeled hydrazine and DFT calculations allowed a reaction path to be proposed. The complexes were characterized by spectroscopy (IR, 1H, 31P, 13C and 15N NMR) and by X-ray crystal structure determination of [Ru(η5-C5H5)(NCCH2Ph)(PPh3){P(OEt)3}]BPh4 (4a).