Mechanism of the transmetalation of organosilanes to gold

Laura Falivene, David J. Nelson, Stéphanie Dupuy, Steven P. Nolan, Albert Poater, Luigi Cavallo

Research output: Contribution to journalArticle

Abstract

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.

LanguageEnglish
Pages60-64
Number of pages5
JournalChemistryOpen
Volume5
Issue number1
Early online date10 Sep 2015
DOIs
Publication statusPublished - 29 Feb 2016

Fingerprint

Gold
Fluorides
Silanes
Silicates
Density functional theory
Chemical activation

Keywords

  • DFT calculations
  • fluoride-free
  • gold catalysis
  • homogeneous catalysis
  • organosilanes
  • transmetalation

Cite this

Falivene, L., Nelson, D. J., Dupuy, S., Nolan, S. P., Poater, A., & Cavallo, L. (2016). Mechanism of the transmetalation of organosilanes to gold. ChemistryOpen, 5(1), 60-64. https://doi.org/10.1002/open.201500172
Falivene, Laura ; Nelson, David J. ; Dupuy, Stéphanie ; Nolan, Steven P. ; Poater, Albert ; Cavallo, Luigi. / Mechanism of the transmetalation of organosilanes to gold. In: ChemistryOpen. 2016 ; Vol. 5, No. 1. pp. 60-64.
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Falivene, L, Nelson, DJ, Dupuy, S, Nolan, SP, Poater, A & Cavallo, L 2016, 'Mechanism of the transmetalation of organosilanes to gold' ChemistryOpen, vol. 5, no. 1, pp. 60-64. https://doi.org/10.1002/open.201500172

Mechanism of the transmetalation of organosilanes to gold. / Falivene, Laura; Nelson, David J.; Dupuy, Stéphanie; Nolan, Steven P.; Poater, Albert; Cavallo, Luigi.

In: ChemistryOpen, Vol. 5, No. 1, 29.02.2016, p. 60-64.

Research output: Contribution to journalArticle

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Falivene L, Nelson DJ, Dupuy S, Nolan SP, Poater A, Cavallo L. Mechanism of the transmetalation of organosilanes to gold. ChemistryOpen. 2016 Feb 29;5(1):60-64. https://doi.org/10.1002/open.201500172