Exploring the reactivity of ru-based metathesis catalysts with a π-acid ligand trans to the Ru-ylidene bond

Albert Poater, Francesco Ragone, Andrea Correa, Luigi Cavallo*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

66 Scopus citations

Abstract

In this work we explore the reactivity induced by coordination of a CO molecule trans to the Ru-ylidene bond of a prototype Ru-olefin metathesis catalyst bearing the N-heterocyclic carbene (NHC) ligand SIMes. Static 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 methylidene group has attacked the proximal aromatic ring of the SIMes ligand leading to a cycloheptatriene through a Buchner ring expansion. Analysis of the relevant molecular orbitals, supported by ab initio molecular dynamics simulations, illuminate the key role of the π-acid CO coordinated trans to the Ru-methylidene bond to promote this reactivity. Based on this result, we investigated to which extent a large set of π-acid groups could promote this deactivating reaction. Results clearly indicate that almost any sufficiently π-acidic group that can approach the Ru center in the sterically crowded position trans to the Ru-methylidene bond can promote this deactivation route.

Original languageEnglish (US)
Pages (from-to)9000-9006
Number of pages7
JournalJournal of the American Chemical Society
Volume131
Issue number25
DOIs
StatePublished - Jul 1 2009

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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