Metal silylenes generated by double silicon-hydrogen activation: key intermediates in the rhodium-catalyzed hydrosilylation of ketones.
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.
Schneider
Nathanaëlle
N
Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
Finger
Markus
M
Haferkemper
Christian
C
Bellemin-Laponnaz
Stéphane
S
Hofmann
Peter
P
Gade
Lutz H
LH