Journal of the American Society for Mass Spectrometry vol:17 issue:6 pages:807-814
date:Univ Mons Hainaut, Organ Chem Lab, B-7000 Mons, Belgium; Katholieke Univ Leuven, Dept Chem, Louvain, Belgium
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. (J Am Soc Mass Spectrom 2006,17, 807-814) (C) 2006 American Society for Mass Spectrometry.