Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Catalyst for the Alcohol Oxidation Reaction

Authors

Chae S. Yi, Marquette UniversityFollow
Tonya N. Zeczycki, University of Wisconsin - Madison
Ilia A. Guzei, University of Wisconsin - Madison

Document Type

Article

Language

eng

Publication Date

2006

Publisher

American Chemical Society

Source Publication

Organometallics

Source ISSN

0276-7333

Original Item ID

DOI: 10.1021/om0510674

Abstract

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy₃)(CO)RuH]₄(μ₄-O)(μ₃-OH)(μ₂-OH)} (1) was synthesized in two steps from the monomeric complex (PCy₃)(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 toward primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C₆H₄CH₂OH (ρ = −0.45) and p-X-C₆H₄CH(OH)CH₃ (ρ = +0.22) (X = OMe, CH₃, H, Cl, CF₃). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH₃] (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.

Comments

Accepted version. Organometallics, Vol. 25, No. 4 (2006): 1047-1051. DOI. © 2006 American Chemical Society. Used with permission.

Recommended Citation

Yi, Chae S.; Zeczycki, Tonya N.; and Guzei, Ilia A., "Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Catalyst for the Alcohol Oxidation Reaction" (2006). Chemistry Faculty Research and Publications. 406.
https://epublications.marquette.edu/chem_fac/406