Insights from Computational Studies on d0 Metal-Catalyzed Alkene and Alkyne Metathesis and Related Reactions

Xavier Solans-Monfort, Christophe Copéret, Odile Eisenstein

Research output: Chapter in BookChapterResearch

4 Citations (Scopus)


© 2015 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved. The computational studies (essentially by DFT methods) of alkene (olefin), and alkyne metathesis by d0 transition metal alkylidene or alkylidyne catalysts are described. The scope of the review includes molecular catalysts (Mo, W, Re), well-defined catalysts (Mo, W, Re, Ta) supported on oxides (silica, alumina) and also heterogeneous catalysts (MoO3, Re2O7 and related) on supports (zeolites, alumina silica:alumina), but also the related nitrile-alkyne cross metathesis and alkane metathesis reactions. Besides structural information about active sites/species, the review describes the reaction pathways of metathesis reaction as well as those leading to catalyst deactivation and side products formation. The influence of the metal and ligands on the energy profiles via a detailed description of transition states and intermediates and the relationship between computational and experimental studies are central aspects of this chapter. The methods used in the studies (molecular, cluster or periodic models, QM vs. QM-MM) are mentioned to present how the models account for the diversity of experimental conditions. While the analogies and differences between the pathways for the various catalysts are discussed, the classical Chauvin mechanism appears general, even if additional steps need to be considered for full description of the pathways and for the understanding of structure - reactivity relationship for d0 alkene metathesis catalysts.
Original languageEnglish
Title of host publicationHandbook of Metathesis - Catalyst Development and Mechanism, 2nd Edition
Editors Grubbs, R. H., Wenzel, A.
Number of pages38
Publication statusPublished - 1 Jan 2015


  • Alkane metathesis
  • Alkene (olefin) metathesis
  • Alkylidene
  • Alkylidyne
  • Alkyne metathesis
  • Cross-metathesis
  • D0 transition metal
  • DFT
  • Deactivation pathways
  • Heterogeneous catalysts
  • Hydrides
  • Imido
  • Mo
  • Molecular catalysts
  • Nitride
  • Oxo
  • Re
  • Reaction pathways
  • Supported (immobilized) catalysts
  • Ta
  • W


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