NHC-copper(I) bifluoride complexes: "Auto-activating" catalysts

Vergote, Thomas;Nahra, Fady;Peeters, Daniel;Riant, Olivier;Leyssens, Tom
(2013) Journal of Organometallic Chemistry — Vol. 730, p. 95-103 (2013)

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Authors
  • Vergote, ThomasUCLouvain
    Author
  • Nahra, FadyUCLouvain
    Author
  • Peeters, DanielUCLouvain
    Author
  • Riant, OlivierUCLouvain
    Author
  • Leyssens, TomUCLouvain
    Author
Abstract
(NHC)copper(I) hydrides catalyse the hydrosilylation of ketones. (NHC)copper(I) (bi)fluoro species were shown to be active catalysts that do not require an activating agent. In this contribution, the selfactivating mechanism of a (NHC)copper(I) (bi)fluoro pre-catalyst has been elucidated by a combined theoretical and experimental study. Experimental NMR studies show the fluorosilane by-product to intervene in the activation mechanism. Thus, bifluoride copper(I) complexes are auto-activating catalysts. Several hypotheses on the activation mechanism have been investigated, and experimental and theoretical results, point towards the formation of a tight ion pair between a difluorosilicate and a cationic copper(I) complex. Results furthermore yield insight into the mechanism of the Cu(I) hydride formation
Affiliations
  • Institution iconUCLouvainSST/IMCN/MOST - Molecules, Solids and Reactivity

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Vergote, T., Nahra, F., Peeters, D., Riant, O., & Leyssens, T. (2013). NHC-copper(I) bifluoride complexes: “Auto-activating” catalysts. Journal of Organometallic Chemistry, 730, 95-103. https://doi.org/10.1016/jorganchem.2012.10.011 (Original work published 2013)