Journal article

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)

George N Khairallah, Charlene Thum, Richard AJ O'Hair



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 ..

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Awarded by ARC

Funding Acknowledgements

We thank the ARC for financial support via Grant No. DP0558430 (to R.A.J.O.) and the VICS for the Chemical Sciences High Performance Computing Facility. We thank Dr. Tom Waters for useful discussions and Ann Jacob for carrying out preliminary calculations on the [HCCMgCl<INF>2</INF>]<SUP>-</SUP> system.