The driving force role of ruthenacyclobutanes

Sai V. C. Vummaleti, Luigi Cavallo, Albert Poater

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

DFT calculations have been used to determine the thermodynamic and kinetic preference for ruthenacyclobutanes resulting from the experimentally proposed interconversion pathways (olefin and alkylidene rotations) through the investigation of cross-metathesis reaction mechanism for neutral Grubbs catalyst, RuCl2(=CHEt)NHC (A), with ethylene and 1-butene as the substrates. Our results show that although the proposed interconversions are feasible due to the predicted low energy barriers (2-6 kcal/mol), the formation of ruthenacyclobutane is kinetically favored over the competitive reactions involving alkylidene rotations. In comparison with catalyst A, the reaction energy profile for cationic Piers catalyst [RuCl2(=CHPCy3)NHC+] (B) is more endothermic in nature with both ethylene and 1-butene substrates.
Original languageEnglish (US)
JournalTheoretical Chemistry Accounts
Volume134
Issue number3
DOIs
StatePublished - Feb 7 2015

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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