title: The benzylperoxyl radical as a source of hydroxyl and phenyl radicals.
abstract: The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O2 is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O-O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H2O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds.
authors.affiliation: Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, 44780 Bochum (Germany). wolfram.sander@rub.de.
authors.forename: Wolfram
authors.initials: W
authors.lastname: Sander
authors.forename: Saonli
authors.initials: S
authors.lastname: Roy
authors.forename: Kenny
authors.initials: K
authors.lastname: Bravo-Rodriguez
authors.forename: Dirk
authors.initials: D
authors.lastname: Grote
authors.forename: Elsa
authors.initials: E
authors.lastname: Sanchez-Garcia
keywords: QM/MM calculations; density functional calculations; matrix isolation; oxidation; radical reactions