Some organometallic chemistry of ruthenium(II)

Article abstract of DOI:10.1016/0022-328X(95)00525-U

Stoichiometric and catalytic reactions of Ru(II) phosphine complexes with alkynes, olefins, and enynes are described.The hydride complex RuCl(CO)H(PPh3)3 (1) reacts with the double bond of a cis-enyne whereas it reacts with triple bonds of trans-enynes.Metathesis of vinyl silanes with olefins are catalyzed by 1 where β-Si elimination is the key step.Dimerizations of t-Bu- and Me3Si-substituted acetylenes into the corresponding butatrienes are catalyzed by Ru(II) active species as studied by isolation of the intermediates.A model reaction for the crucial step of the catalytic cycle, formation of a Ru vinylidene complex from acetylene, has been fully simulated by ab initio-MO calculations.Keywords: Ruthenium; Olefins; Alkynes; Catalysis; Crystal structure; MO calculations