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Published on: January 19, 2016
Decarboxylation of metastable methyl benzoate molecular ions
Noémie Dechamps1, Robert Flammang1, Pascal Gerbaux2
1Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium.
Abstract:
By using a combination of mass spectrometric methodologies and density functional theory calculations [DFT/B3LYP/6-311 ++ G(d, p)], it is proposed that the decarboxylation of metastable methyl benzoate molecular ions occurs via distonic and ion-neutral complex (INC) intermediates. The same INC involving a complex between the benzyl radical and protonated carbon dioxide is also generated upon decarboxylation of metastable phenylacetic acid molecular ions. Internal proton transfer within the INC produces in fine a mixture of toluene and isotoluene radical cations.
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