A Second Metal Center Enhances the Reactivity of an Organomagnesate: Comparison of the Gas-Phase Reactions of Water with [RCCMgCl2](-) and [RCCMg2Cl4](-) (R = H, Ph)

Abstract

The gas-phase formation and hydrolysis reactions of the mononuclear and binuclear organomagnesate ions [RCCMgnCl2n]- (where R = H, Ph and n = 1, 2) were studied using a combination of ion trap mass spectrometry based experiments and DFT calculations. The organomagnesates were formed via decarboxylation of the carboxylates [RCCCO2Mg nCl2n]-. The binuclear organomagnesates [RCCMg2Cl4]- were found to be at least 5 times more reactive than the mononuclear organomagnesates [RCCMgCl2] - (where R = H, Ph). The DFT calculations highlight the role that a second magnesium center can have on both the formation and reaction of an organomagnesate. Thus, DFT calculations reveal that while decarboxylation ..