Dimethylcuprate Undergoes a Dyotropic Rearrangement

Abstract

All change! Comparison of the gas-phase decomposition reactions of [CH3CuCH3]− and [CH3AgCH3]− reveals that [CH3CuCH3]− undergoes a competition between a dyotropic rearrangement and bond homolysis, whilst [CH3AgCH3]− only undergoes bond homolysis. Ab initio calculations reveal that the different behavior in [CH3AgCH3]− stems from both the lowering of the homolytic bond dissociation energy and an increase in dyotropic rearrangement activation energy.