title: Metal silylenes generated by double silicon-hydrogen activation: key intermediates in the rhodium-catalyzed hydrosilylation of ketones.
abstract: Rhodium silylenes, which are generated by double Si-H activation at the metal, are involved in a low-activation-barrier mechanism of the hydrosilylation of ketones with R(2)SiH(2). A DFT-based study of reaction mechanisms accounts for the experimental observations, notably the rate enhancement for R(2)SiH(2) over R(3)SiH and an inverse kinetic isotope effect.
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
authors.forename: Nathanaëlle
authors.initials: N
authors.lastname: Schneider
authors.forename: Markus
authors.initials: M
authors.lastname: Finger
authors.forename: Christian
authors.initials: C
authors.lastname: Haferkemper
authors.forename: Stéphane
authors.initials: S
authors.lastname: Bellemin-Laponnaz
authors.forename: Peter
authors.initials: P
authors.lastname: Hofmann
authors.forename: Lutz H
authors.initials: LH
authors.lastname: Gade