Faculty Collaboration Database

Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction. Organometallics 2006;25(4):1047-1051

Date

08/30/2008

Pubmed ID

18726005

Pubmed Central ID

PMC2519863

DOI

10.1021/om0510674

Scopus ID

2-s2.0-33644522411 (requires institutional sign-in at Scopus site)   36 Citations

Abstract

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.

Author List

Yi CS, Zeczycki TN, Guzei IA

Author

Chae Yi PhD Professor, Inorganic and Organometallic Chemistry, Homogeneous Catalysis in the Chemistry department at Marquette University