Document Type
Article
Language
eng
Publication Date
2008
Publisher
American Chemical Society
Source Publication
Organometallics
Source ISSN
0276-7333
Abstract
The tetranuclear ruthenium-oxo-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was found to be a highly cooperative catalyst for the nitrile hydration reaction. The cooperative mechanism of the hydration of benzonitrile was established by Hill inhibition kinetics. The treatment of a nitrile substrate with complex 1 led to the catalytically relevant nitrile-coordinated tetraruthenium complex 3. The X-ray structure of the nitrile-coordinated complex 3 showed a considerably “relaxed” tetrameric core structure compared to that of 1. The hydration of para-substituted benzonitriles p-X-C6H4CN with an electron-withdrawing group (X = Cl, Br, CO2H, CF3) exhibited cooperative kinetics, as indicated by the sigmoidal saturation kinetics, while the hydration of nitriles with an electron-donating group (X = OH, OMe, t-Bu, CH3) obeyed Michaelis–Menten saturation kinetics. The formation of a ruthenium hydride species was observed during the hydration of methacrylonitrile, and its monomeric nature was established by using DOSY NMR techniques.
Recommended Citation
Yi, Chae S.; Zeczycki, Tonya N.; and Lindeman, Sergey V., "Kinetic, Spectroscopic, and X-Ray Crystallographic Evidence for the Cooperative Mechanism of the Hydration of Nitriles Catalyzed by a Tetranuclear Ruthenium-μ-oxo-μ-hydroxo Complex" (2008). Chemistry Faculty Research and Publications. 621.
https://epublications.marquette.edu/chem_fac/621
Comments
Accepted version. Organometallics, Vol. 27, No. 9 (2008): 2030-2035. DOI. © 2008 American Chemical Society. Used with permission.