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Mechanism of the Transmetalation of Organosilanes to Gold

Density functional theory (DFT) calculations were carried outto study the reaction mechanism of the first transmetalation oforganosilanes to gold as a cheap fluoride-free process. The versatilegold(I) complex [Au(OH)(IPr)] permits very straightforwardaccess to a series of aryl-, vinyl-, and alkylgold silanolatesby reaction with the appropriate silane reagent. These silanolatecompounds are key intermediates in a fluoride-free processthat results in the net transmetalation of organosilanes togold, rather than the classic activation of silanes as silicatesusing external fluoride sources. However, here we proposethat the gold silanolate is not the active species (as proposedduring experimental studies) but is, in fact, a resting stateduring the transmetalation process, as a concerted step is preferred

A. P. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

Wiley Open Access

Author: Falivene, Laura
Nelson, David J.
Dupuy, St茅phanie
Nolan, Steven P.
Poater Teixidor, Albert
Cavallo, Luigi
Abstract: Density functional theory (DFT) calculations were carried outto study the reaction mechanism of the first transmetalation oforganosilanes to gold as a cheap fluoride-free process. The versatilegold(I) complex [Au(OH)(IPr)] permits very straightforwardaccess to a series of aryl-, vinyl-, and alkylgold silanolatesby reaction with the appropriate silane reagent. These silanolatecompounds are key intermediates in a fluoride-free processthat results in the net transmetalation of organosilanes togold, rather than the classic activation of silanes as silicatesusing external fluoride sources. However, here we proposethat the gold silanolate is not the active species (as proposedduring experimental studies) but is, in fact, a resting stateduring the transmetalation process, as a concerted step is preferred
A. P. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Document access: http://hdl.handle.net/2072/268705
Language: eng
Publisher: Wiley Open Access
Rights: Attribution 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by/3.0/es/
Subject: Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacci贸 (Qu铆mica)
Reaction mechanisms (Chemistry)
Title: Mechanism of the Transmetalation of Organosilanes to Gold
Type: info:eu-repo/semantics/article
Repository: Recercat

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