Open AccessMechanism of the Transmetalation of Organosilanes to Gold
Author(s) -
Falivene Laura,
Nelson David J.,
Dupuy Stéphanie,
Nolan Steven P.,
Poater Albert,
Cavallo Luigi
Publication year - 2016
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201500172
Subject(s) - transmetalation , reagent , silanes , chemistry , silane , combinatorial chemistry , fluoride , aryl , density functional theory , reaction mechanism , organic chemistry , computational chemistry , catalysis , inorganic chemistry , alkyl
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.