Mechanism of Ruthenium-Catalyzed Olefin Metathesis Reactions from a Theoretical Perspective
- 1 July 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (30) , 8965-8973
- https://doi.org/10.1021/ja016772s
Abstract
This paper presents a density functional theory study of the ruthenium-catalyzed olefin metathesis reactions. The ligand binding energy has been calculated in the first generation of Grubbs-type (PCy3)2Cl2RuCHPh (pre)catalyst, as well as in the heteroleptic (pre)catalytic systems in which a N-heterocyclic carbene, NHC, ligand substitutes a single phosphine. In agreement with experiments PCy3 coordinates more strongly to Ru in the heteroleptic (pre)catalysts than in the Grubbs-type (pre)catalyst. Moreover, ethene coordination and insertion into the Ru−alkylidene bond in the above-mentioned systems, as well as in the Hofmann type catalytic system with a cis-coordinated phosphane ligand, has been studied. The calculated insertion barrier for the NHC systems are lower than that of the (PCy3)2Cl2RuCHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.Keywords
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