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Mechanism of ketone hydrosilylation using NHC–Cu(I) catalysts: a computational study

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Theoretical Chemistry in Belgium

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 6))

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Abstract

The plausibility of the catalytic cycle suggested for the hydrosilylation of ketones by (NHC) copper( I) hydrides has been investigated by a theoretical DFT study. Model systems yield the necessary insight into the intrinsic reactivity of the system. Computations show the activation of the copper fluoride pre-catalyst, as well as both steps of the catalytic cycle to involve a 4-center metathesis transition state as suggested in the literature. These results show the reaction to be favored by the formation of van der Waals complexes resembling the transition states. Stabilizing electrostatic interactions between those atoms involved in the bond-breaking and bondforming processes induces the formation of these latter. Both steps of the actual catalytic cycle show a free energy barrier of about 14.5 kcal/mol for the largest NHC ligands, with respect to the isolated reactants, hereby confirming the plausibility of the suggested cycle. The large overall exothermicity of the catalytic cycle of about 35 kcal/mol is in agreement with experimental observations.

Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium

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Authors and Affiliations

  1. Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, Place Louis Pasteur 1, 1348, Louvain-la-Neuve, Belgium

    Thomas Vergote, Thomas Gathy, Fady Nahra, Olivier Riant, Daniel Peeters & Tom Leyssens

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  1. Thomas Vergote
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  2. Thomas Gathy
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  3. Fady Nahra
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  4. Olivier Riant
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  6. Tom Leyssens
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Correspondence to Tom Leyssens .

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Editors and Affiliations

  1. Laboratory of Theoretical Chemistry, University of Namur, Namur, Belgium

    Benoît Champagne

  2. Research Group of Theoretical Chemistry and Molecular Modeling, Hasselt University, Diepenbeek, Belgium

    Michael S. Deleuze

  3. Faculteit Wetenschappen, Free University of Brussels, Brussels, Belgium

    Frank De Proft

  4. Laboratory of Crystal Engineering Inst.of Condensed Matter and Nanoscience, Catholic University of Louvain, Louvain-La-Neuve, Belgium

    Tom Leyssens

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Vergote, T., Gathy, T., Nahra, F., Riant, O., Peeters, D., Leyssens, T. (2014). Mechanism of ketone hydrosilylation using NHC–Cu(I) catalysts: a computational study. In: Champagne, B., Deleuze, M., De Proft, F., Leyssens, T. (eds) Theoretical Chemistry in Belgium. Highlights in Theoretical Chemistry, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41315-5_12

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