title: Mechanism of the dehydrogenative silylation of alcohols catalyzed by cationic gold complexes: an experimental and theoretical study.
abstract: The catalytic activity both of cationic [(XDPP)Au][X] (XDPP = bis-2,5-diphenylphosphole xantphos X = BF(4)) and of the isolated gold hydride complex [(XDPP)(2)Au(2)H][OTf] in the dehydrogenative silylation process is presented. A parallel theoretical study using density functional theory revealed a mechanism involving the counter anion as a co-catalyst, which was experimentally confirmed by testing various counterions (X = OTf, NTf(2), PF(6)). Finally, a "Au(2)H(+)" species was determined as the intermediate during the catalytic cycle, which correlates well with the experimental findings on the first example of catalytic activity of an isolated "Au-H" complex.
authors.affiliation: Laboratoire Hétéroéléments et Coordination, UMR CNRS 7653, DCPH, Département de Chimie, Ecole Polytechnique, 91128 Palaiseau Cedex, France.
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Labouille
authors.forename: Aurélie
authors.initials: A
authors.lastname: Escalle-Lewis
authors.forename: Yves
authors.initials: Y
authors.lastname: Jean
authors.forename: Nicolas
authors.initials: N
authors.lastname: Mézailles
authors.forename: Pascal
authors.initials: P
authors.lastname: Le Floch