Journal article

Unimolecular Reactions of Organocuprates and Organoargentates

Nicole J Rijs, Richard AJ O'Hair

ORGANOMETALLICS | AMER CHEMICAL SOC | Published : 2010

Abstract

The gas-phase fragmentation reactions of the group 11 organometallates [CH3MR]-(R = CH3- CH2, CH3CH 2CH2, (CH3)2CH, (CH 3)3C, CH2CHCH2, PhCH2, Ph, M = Cu, Ag) and [CH3CH2- CuCH2CH 3]-were studied by density functional theory (DFT) calculations and, for those accessible in the gas phase, via collision-induced dissociation (CID) and selected deuterium labeling experiments. The mixed metallates [CH 3MR]- were found to fragment via a diverse set of pathways, including bond homolysis, bond heterolysis, and β elimination. A 1, 2-dyotropic rearrangement was observed for R = Ph. DFT calculations suggest that the M-C bond energy, the availability of metal orbitals for π-bonding, and the nature of the..

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University of Melbourne Researchers