Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 128, Issue 14, Pages 4756-4765Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja057998o
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Au(III)-Schiff base complexes are active hydrogenation catalysts, giving turnover frequencies similar to those of the corresponding complexes of Pd(II), which has the same d(8) electronic structure as Au(III). The mechanism of the reaction has been studied in detail by a combination of kinetic experiments and theoretical calculations. It is predicted and tested that the nature of the solvent plays a critical role for the heterolytic cleavage of H-2 (controlling step). Taking this into account, and by properly selecting the nature of solid supports (polarity and proton-donating ability), it was possible to strongly increase the activity of the homogeneous Au(III) and Pd(II) catalysts by grafting them onto the surface.
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