000118312 001__ 118312
000118312 005__ 20190527123502.0
000118312 02470 $$2DAR$$a11786
000118312 02470 $$a000252019500046$$2ISI
000118312 0247_ $$2doi$$a10.1021/ic701773a
000118312 037__ $$aARTICLE
000118312 245__ $$aReactivity and Catalytic Activity of a Robust Ruthenium(II)-Triphos Complex
000118312 269__ $$a2008
000118312 260__ $$c2008
000118312 336__ $$aJournal Articles
000118312 520__ $$aThe ruthenium(II)-triphos acetato complex [RuCl(OAc)(k3-triphos)] (triphos = (PPh2CH2)3CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H2, 50 °C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k3-triphos)] is much less air sensitive and high catalytic activities were achieved when catalyst samples were prepd. without exclusion of air or moisture. Substitution of the acetato ligand can be effected by treatment of acid, affording [Ru2(m-Cl)3(k3-triphos)2]Cl and [RuCl(k3-triphos)]2(BF4)2 with aq. HCl and [Et2OH]BF4, resp., or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k2-dmpm)(k3-triphos)]PF6 (dmpm = PMe2CH2PMe2). A hydride complex, [RuHCl(k3-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc)(k3-triphos)] and [RuH(OAc)(k3-triphos)] and supported by a computational anal. The solid-state structures of [RuCl(OAc)(k3-triphos)], [RuCl(k3-triphos)]2(BF4)2, and [RuCl(k2-dmpm)(k3-triphos)]PF6 have been established by X-ray diffraction.
000118312 700__ $$0240381$$g161826$$aChaplin, Adrian B.
000118312 700__ $$aDyson, Paul J.$$g149418$$0240015
000118312 773__ $$j47$$tInorganic Chemistry$$k1$$q381-390
000118312 909C0 $$xU9$$0252010$$pLCOM
000118312 909CO $$pSB$$particle$$ooai:infoscience.tind.io:118312
000118312 937__ $$aLCOM-ARTICLE-2008-046
000118312 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000118312 980__ $$aARTICLE