Decarboxylation of metastable methyl benzoate molecular ions.
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.
Dechamps
Noémie
N
Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium.
Flammang
Robert
R
Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium.
Gerbaux
Pascal
P
Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium. pascal.gerbaux@umh.ac.be.
Nam
Pham-Cam
PC
Department of Chemistry, University of Leuven, Leuven, Belgium.
Nguyen
Minh-Tho
MT
Department of Chemistry, University of Leuven, Leuven, Belgium.