Mechanism of the Transmetalation of Organosilanes to Gold.
Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the first transmetalation of organosilanes to gold as a cheap fluoride-free process. The versatile gold(I) complex [Au(OH)(IPr)] permits very straightforward access to a series of aryl-, vinyl-, and alkylgold silanolates by reaction with the appropriate silane reagent. These silanolate compounds are key intermediates in a fluoride-free process that results in the net transmetalation of organosilanes to gold, rather than the classic activation of silanes as silicates using external fluoride sources. However, here we propose that the gold silanolate is not the active species (as proposed during experimental studies) but is, in fact, a resting state during the transmetalation process, as a concerted step is preferred.
KAUST Catalysis Center Physical Sciences and Engineering Division King Abdullah University of Science and Technology Thuwal 23955-6900 Saudi Arabia.
Laura
L
Falivene
WestCHEM Department of Pure & Applied Chemistry University of Strathclyde Thomas Graham Building 295 Cathedral Street Glasgow G1 1XL UK.
David J
0000-0002-9461-5182
DJ
Nelson
EaStCHEM School of Chemistry University of St. Andrews North Haugh St. Andrews Fife KY16 9ST UK.
Stéphanie
S
Dupuy
EaStCHEM School of Chemistry University of St. Andrews North Haugh St. Andrews Fife KY16 9ST UK; Chemistry Department College of Science King Saud University P.O. Box 2455 Riyadh 11451 Saudi Arabia.
Steven P
SP
Nolan
Institut de Química Computacional i Catàlisi and Departament de Química Universitat de Girona Campus Montilivi 17071 Girona Catalonia Spain.
Albert
0000-0002-8997-2599
A
Poater
KAUST Catalysis Center Physical Sciences and Engineering Division King Abdullah University of Science and Technology Thuwal 23955-6900 Saudi Arabia.
Luigi
L
Cavallo
DFT calculations; fluoride-free; gold catalysis; homogeneous catalysis; organosilanes; transmetalation