title: 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.
authors.affiliation: School of Chemistry, University of Wollongong, Wollongong, NSW 2522, Australia. adamt@uow.edu.au.
authors.forename: Matthew B
authors.initials: MB
authors.lastname: Prendergast
authors.forename: Phillip A
authors.initials: PA
authors.lastname: Cooper
authors.forename: Benjamin B
authors.initials: BB
authors.lastname: Kirk
authors.forename: Gabriel
authors.initials: G
authors.lastname: da Silva
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Blanksby
authors.forename: Adam J
authors.initials: AJ
authors.lastname: Trevitt