Deactivation of Ru-benzylidene Grubbs catalysts active in olefin metathesis

Albert Poater, Luigi Cavallo*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

In this work, we explore the reactivity induced by coordination of a CO molecule trans to the Ru-benzylidene bond of a prototype Ru-olefin metathesis catalyst bearing a N-heterocyclic carbene (NHC) ligand. DFT calculations indicate that CO binding to the Ru center promotes a cascade of reactions with very low-energy barriers that lead to the final crystallographically characterized product, in which the original benzylidene group has attacked the proximal aromatic ring of the ligand leading to a cycloheptatriene ring through a Buchner ring expansion. In conclusion, the overall mechanism is best described as a carbene insertion into a C-C bond of the aromatic N-substituent of the NHC ligand, forming a cyclopropane ring. This cyclopropanation step is followed by a Buchner ring expansion reaction, leading to the experimentally observed product presenting a cycloheptatriene ring.

Original languageEnglish (US)
Pages (from-to)1-6
Number of pages6
JournalTheoretical Chemistry Accounts
Volume131
Issue number3
DOIs
StatePublished - Mar 1 2012

Keywords

  • Cyclopropanation
  • Deactivation
  • Homogeneous catalysis
  • N-heterocyclic carbene
  • Olefins metathesis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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