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Journal Article

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons101523

Bravo-Rodriguez,  Kenny
Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons101503

Sanchez-Garcia,  Elsa
Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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chem_201402459_sm_miscellaneous_information.pdf
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Citation

Sander, W., Roy, S., Bravo-Rodriguez, K., Grote, D., & Sanchez-Garcia, E. (2014). The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals. Chemistry – A European Journal, 20(40), 12917-12923. doi:10.1002/chem.201402459.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-A813-3
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.