Titre du document / Document title

Analysis of an Unprecedented Mechanism for the Catalytic Hydrosilylation of Carbonyl Compounds

Auteur(s) / Author(s)

NOLIN Kristine A. ; KRUMPER Jennifer R. ; PLUTH Michael D. ; BERGMAN Robert G. ; TOSTE F. Dean ;

Résumé / Abstract

This work details an in-depth evaluation of an unprecedented mechanism for the hydrosilylation of carbonyl compounds catalyzed by (PPh₃)₂Re(O)₂l. The proposed mechanism involves addition of a silane Si-H bond across one of the rhenium-oxo bonds to form siloxyrhenium hydride intermediate 2 that reacts with a carbonyl substrate to generate siloxyrhenium alkoxide 4, which, in turn, affords the silyl ether product. Compelling evidence for the operation of this pathway includes the following: (a) isolation and structural characterization by X-ray diffraction of siloxyrhenium hydride intermediate 2, (b) demonstration of the catalytic competence of intermediate 2 in the hydrosilylation reaction, (c) ¹H and ³¹F{¹H} NMR and ESI-MS evidence for single-turnover conversion of 2 into 1, (d) observation of intermediate 2 in the working catalyst system, and (e) kinetic analysis of the catalytic hydrosilylation of carbonyl compounds by 1.

Revue / Journal Title

Journal of the American Chemical Society   ISSN 0002-7863   CODEN JACSAT 

Source / Source

2007, vol. 129, n^o47, pp. 14684-14696 [13 page(s) (article)]

Langue / Language

Anglais

Editeur / Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1879) (Revue)

Localisation / Location

INIST-CNRS, Cote INIST : 551, 35400017429383.0370