Publication

Reactivity and Catalytic Activity of a Robust Ruthenium(II)-Triphos Complex

Paul Joseph Dyson
2008
Journal paper
Abstract

The 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.

About this result
This page is automatically generated and may contain information that is not correct, complete, up-to-date, or relevant to your search query. The same applies to every other page on this website. Please make sure to verify the information with EPFL's official sources.

Graph Chatbot

Chat with Graph Search

Ask any question about EPFL courses, lectures, exercises, research, news, etc. or try the example questions below.

DISCLAIMER: The Graph Chatbot is not programmed to provide explicit or categorical answers to your questions. Rather, it transforms your questions into API requests that are distributed across the various IT services officially administered by EPFL. Its purpose is solely to collect and recommend relevant references to content that you can explore to help you answer your questions.