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Reactivity and catalytic activity of a robust ruthenium(II)−triphos complex

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Chaplin, Adrian B. and Dyson, Paul J. (2008) Reactivity and catalytic activity of a robust ruthenium(II)−triphos complex. Inorganic Chemistry, Vol.47 (No.1). pp. 381-390. doi:10.1021/ic701773a ISSN 0020-1669.

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Official URL: http://dx.doi.org/10.1021/ic701773a

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Abstract

The ruthenium(II)-triphos acetatc, complex [RuCl(OAc)(k(3)-triphos)] (triphos = (PPh2CH2)(3)CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H-2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k(3)-triphos)] is much less air sensitive and 14 high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetatc, ligand can be effected by treatment of acid, affording [Ru-2(mu-Cl)(3)(k(3)-triphos)(2)]Cl and [RuCl(k(3)-triphos)](2)(BF4)(2) with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k(2)-dMPM)(k(3)-triphos)]PF6 (dmpm = PMe(2)CH(2)PMe2). A hydride complex, [RuHCl (k(3)-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) (k(3)-triphos)] and [RuH(OAc)(k(3)-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(k(3)-triphos)], [RuCl(k(3)-triphos)](2)(BF4)(2), and [RUCl(k(2)-dmpm)(k(3)-triphos)]PF6 have been established by X-ray diffraction.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Ruthenium, Transition metal complexes, Transition metal catalysts, Hydrogenation, Alkenes
Journal or Publication Title: Inorganic Chemistry
Publisher: American Chemical Society
ISSN: 0020-1669
Official Date: 7 January 2008
Dates:
DateEvent
7 January 2008Published
Volume: Vol.47
Number: No.1
Page Range: pp. 381-390
DOI: 10.1021/ic701773a
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: École polytechnique fédérale de Lausanne [Swiss Federal Institute of Technology (Lausanne, Switzerland)] (EPFL), Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung [Swiss National Science Foundation] (SNF)

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