Issue 47, 2013

Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations

Abstract

The reactions of distonic 4-(N,N,N-trimethylammonium)-2-methylphenyl and 5-(N,N,N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O2 to form [M + O2+ and [M + O2 − OH]˙+ ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N,N,N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5-H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates ˙OH to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O2 reaction, thus serving as a plausible source of ˙OH radicals in combustion environments.

Graphical abstract: Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations

Supplementary files

Article information

Article type
Paper
Submitted
01 Sep 2013
Accepted
21 Oct 2013
First published
29 Oct 2013

Phys. Chem. Chem. Phys., 2013,15, 20577-20584

Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations

M. B. Prendergast, P. A. Cooper, B. B. Kirk, G. D. Silva, S. J. Blanksby and A. J. Trevitt, Phys. Chem. Chem. Phys., 2013, 15, 20577 DOI: 10.1039/C3CP53690D

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