Potential energy surface for (retro-)cyclopropanation: Metathesis with a cationic gold complex

Alexey Fedorov, Laurent Batiste, Andreas Bach, David M. Birney, Peter Chen

Research output: Contribution to journalArticlepeer-review

57 Scopus citations


The gas-phase cyclopropanation and apparent metathesis reactivity of ligand-supported gold arylidenes with electron-rich olefins is explained by quantum-chemical calculations. A deep potential minimum corresponding to a metal-bound cyclopropane adduct is in agreement with the measured absolute energies of the cyclopropanation and metathesis channels and is also consistent with previously reported electronic effects of arylidenes and supporting phosphorus ylid ligands on the product ratios. In the gas phase, the rate-determining step for the cyclopropanation is dissociation of the Lewis-acidic metal fragment, whereas the metathesis pathway features several rate-limiting transition states that are close in energy to the final product dissociation and hence contribute to the overall reaction rate. Importantly, the presented potential energy surface also accounts for the recently reported gold-catalyzed solution-phase retro-cyclopropanation reactivity.

Original languageEnglish
Pages (from-to)12162-12171
Number of pages10
JournalJournal of the American Chemical Society
Issue number31
StatePublished - Aug 10 2011


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