Journal article

Direct versus Water-Mediated Protodecarboxylation of Acetic Acid Catalyzed by Group 10 Carboxylates, [(phen)M(O2CCH3)]( )

Matthew Woolley, George N Khairallah, Gabriel da Silva, Paul S Donnelly, Richard AJ O'Hair



The gas-phase protodecarboxylation of acetic acid catalyzed by group 10 metal complexes was examined using a combination of multistage mass spectrometry experiments in an ion trap mass spectrometer, DFT calculations, and theoretical kinetic modeling. Two related catalytic cycles sharing two common intermediates were examined. The entry points to both cycles are the metal acetate complexes [(phen)M(O2CCH3)]+ (where phen = 1,10-phenanthroline), which were formed via direct electrospray ionization of solutions of the complexes [(phen)M(O2CCH3)2] in water. Step 1 of both cycles involves decarboxylation of [(phen)M(O2CCH3)]+ under collision-induced dissociation (CID) conditions to form the organo..

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Awarded by ARC

Funding Acknowledgements

We thank the ARC for financial support via grant DP110103844 (to R.A.J.O. and G.N.K.), DP1096134 (to G.N.K.), and DP110103889, DP130100862, and FT130101304 (to G.d.S.), and through the ARC CoE program. M.W. thanks the Faculty of Science for a Melbourne Research Scholarship. The authors gratefully acknowledge the generous allocation of computing time from the Victorian Partnership for Advanced Computing (VPAC) Facility.