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Realistic modeling of ruthenium-catalyzed transfer hydrogenation.

Authors
  • Handgraaf, Jan-Willem
  • Meijer, Evert Jan
Type
Published Article
Journal
Journal of the American Chemical Society
Publication Date
Mar 21, 2007
Volume
129
Issue
11
Pages
3099–3103
Identifiers
PMID: 17319655
Source
Medline
License
Unknown

Abstract

We report the first computational study of a fully atomistic model of the ruthenium-catalyzed transfer hydrogenation of formaldehyde and the reverse reaction in an explicit methanol solution. Using ab initio molecular dynamics techniques, we determined the thermodynamics, mechanism, and electronic structure along the reaction path. To assess the effect of the solvent quantitatively, we make a direct comparison with the gas-phase reaction. We find that the energy profile in solution bears little resemblance to the profile in the gas phase and a distinct solvation barrier is found: the activation barriers in both directions are lowered and the concerted hydride and proton transfer in the gas phase are converted into a sequential mechanism in solution with the substrate appearing as methoxide-like intermediate. Our results indicate that besides the metal-ligand bifunctional mechanism, as proposed by Noyori, also a concerted solvent-mediated mechanism is feasible. Our study gives a new perspective of the active role a solvent can have in transition-metal-catalyzed reactions.

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