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  The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

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.

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chem_201402459_sm_miscellaneous_information.pdf (Supplementary material), 2MB
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chem_201402459_sm_miscellaneous_information.pdf
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Supporting Information
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Copyright Date:
2014
Copyright Info:
Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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 Creators:
Sander, Wolfram1, Author
Roy, Saonli1, Author
Bravo-Rodriguez, Kenny2, Author              
Grote, Dirk1, Author
Sanchez-Garcia, Elsa2, Author              
Affiliations:
1Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, 44780 Bochum (Germany), ou_persistent22              
2Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1950289              

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Free keywords: density functional calculations; matrix isolation; oxidation; radical reactions; QM/MM calculations
 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.

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Language(s): eng - English
 Dates: 2014-03-032014-08-212014-09-26
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201402459
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 20 (40) Sequence Number: - Start / End Page: 12917 - 12923 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058