Matthew J. Woolley, George N. Khairallah, G. Silva
Sep 29, 2014
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Journal
Organometallics
Abstract
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 organometallic species [(phen)M(CH3)]+. The ease of decarboxylation follows the order Pd > Pt > Ni as determined via energy-resolved CID experiments, which is in agreement with the activation energies for decarboxylation estimated from DFT calculations. Step 2 of cycle 1 involves an ion–molecule reaction between [(phen)M(CH3...