The gas-phase fragmentation reactions of the group 11 organometallates [CH3M (R = CH3C CH3CHCH2, (CH3)(2)CH, (CH3)(3)C, CH2CHCH2 PhCH2, Ph, M = Cu, Ag) and [CH3CH2-CuCH2CH3](-) 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 [CH3MR](-) were found to fragment via a diverse set of pathways, including bond homolysis, bond heterolysis, and beta-hydride elimination. A 1,2-dyotropic rearrangement was observed for R = Ph. D FT calculations suggest that the M C bond energy, the availability of metal orbitals for pi-bonding, and the nature of the ligand R group substituents are the main factors that control the observed reactivity. Comparisons with the known solution-phase reactivity of organocopper and organosilver species are made.
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