Decarboxylation of metastable methyl benzoate molecular ions

Noémie Dechamps; Robert Flammang; Pascal Gerbaux; Pham-Cam Nam; Minh-Tho Nguyen

doi:10.1016/j.jasms.2006.02.015

Decarboxylation of metastable methyl benzoate molecular ions

J Am Soc Mass Spectrom. 2006 Jun;17(6):807-814. doi: 10.1016/j.jasms.2006.02.015. Epub 2006 Apr 17.

Authors

Noémie Dechamps¹, Robert Flammang¹, Pascal Gerbaux², Pham-Cam Nam³, Minh-Tho Nguyen³

Affiliations

¹ Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium.
² Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium. pascal.gerbaux@umh.ac.be.
³ Department of Chemistry, University of Leuven, Leuven, Belgium.

PMID: 16603373
DOI: 10.1016/j.jasms.2006.02.015

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.