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Gold hydride is a rare transition-metal species. Despite the fact that gold hydrides may be key intermediates in several gold-catalyzed reactions, their chemical properties are not well understood. We report the synthesis, characterization, and catalytic properties of the gold(I) hydride species that play an important role in a gold(I)-catalyzed dehydrogenative alcohol silylation. Tricoordinated complexes AuCl(xantphos) ( 1a ) and AuCl(xy-xantphos) ( 1b ) were prepared and characterized by 1 H and 31 P{ 1 H} NMR measurements and X-ray crystallography. Gold(I) hydride species 6b generated from the reaction between 1b and PhMe 2 SiH ( 4b ) in CDCl 3 was characterized by 1 H and 31 P NMR measurements and ESI-MS spectrometry. NMR and kinetic studies revealed that the reaction mechanism involves the gold(I) hydride species as a key intermediate. The high catalytic activities of 1a and 1b in dehydrogenative alcohol silylation are explained by the stability of the tricoordinated chelating structure and the activation of the Au−Cl bond induced by the stereoelectronic effect of the coordinating phosphorus atoms. This study reports the first example of a gold(I) hydride complex that exhibits catalytic activity.
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Ito et al. (2009) studied this question.
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