Gas-phase synthesis of the homo and hetero organocuprate anions [MeCuMe]-, [EtCuEt]-, and [MeCuR]-

Abstract

The homocuprates [MeCuMe]- and [EtCuEt]- were generated in the gas phase by double decarboxylation of the copper carboxylate centers [MeCO2CuO2CMe]- and [EtCO 2CuO2CEt]-, respectively. The same strategy was explored for generating the heterocuprates [MeCuR]- from [MeCO 2CuO2CR]- (R = Et, Pr, tPr, tBu, allyl, benzyl, Ph). The formation of these organocuprates was examined by multistage mass spectrometry experiments, including collision-induced dissociation and ion-molecute reactions, and theoretically by density functional theory. A number of side reactions were observed to be in competition with the second stage of decarboxylation, including loss of the anionic carboxylate ligand and loss of..