"Kinetic, Spectroscopic, and X-Ray Crystallographic Evidence for the Co" by Chae S. Yi, Tonya N. Zeczycki et al.
 

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]44-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.

Comments

Accepted version. Organometallics, Vol. 27, No. 9 (2008): 2030-2035. DOI. © 2008 American Chemical Society. Used with permission.

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