Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective

Luigi Cavallo

doi:10.1021/ja016772s

Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective

Luigi Cavallo^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

253 Scopus citations

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)₂-Cl₂Ru=CHPh (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)₂Cl₂Ru=CHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.

Original language	English (US)
Pages (from-to)	8965-8973
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	124
Issue number	30
DOIs	https://doi.org/10.1021/ja016772s
State	Published - Jul 31 2002
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective",

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)2-Cl2Ru=CHPh (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)2Cl2Ru=CHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.",

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T1 - Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective

AU - Cavallo, Luigi

PY - 2002/7/31

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N2 - 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)2-Cl2Ru=CHPh (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)2Cl2Ru=CHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.

AB - 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)2-Cl2Ru=CHPh (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)2Cl2Ru=CHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.

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JO - Journal of the American Chemical Society

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Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective

Abstract

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