Mechanism of ketone hydrosilylation using NHC-Cu(I) catalysts: a computational study
(2012) Theoretical Chemistry Accounts : theory, computation and modeling — Vol. 131, p. 1253 (2012)
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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 bond-forming 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.
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Citations
Vergote, T., Gathy, T., Nahra, F., Riant, O., Peeters, D., & Leyssens, T. (2012). Mechanism of ketone hydrosilylation using NHC-Cu(I) catalysts: a computational study. Theoretical Chemistry Accounts : theory, computation and modeling, 131, 1253. https://doi.org/10.1007/s00214-012-1253-4 (Original work published 2012)