Unexpected Acid Catalysis in Reactions of Peroxyl Radicals with Phenols

Weak organic acids in millimolar concentrations increase the reactivity of peroxyl radicals with common phenolic antioxidants dramatically. This counterintuitive phenomenon relies on a substantially different reaction mechanism from that in the absence of an acid: rate‐determining electron transfer...

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Published inAngewandte Chemie (International ed.) Vol. 48; no. 44; pp. 8348 - 8351
Main Authors Valgimigli, Luca, Amorati, Riccardo, Petrucci, Silvia, Pedulli, Gian Franco, Hu, Di, Hanthorn, Jason J, Pratt, Derek A
Format Journal Article
LanguageEnglish
Published Weinheim Wiley-VCH Verlag 19.10.2009
WILEY-VCH Verlag
WILEY‐VCH Verlag
Subjects
Acids - chemistry
antioxidants
Catalysis
EPR spectroscopy
hydrogen transfer
Kinetics
Peroxides - chemistry
Phenols - chemistry
proton-coupled electron transfer
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Summary:Weak organic acids in millimolar concentrations increase the reactivity of peroxyl radicals with common phenolic antioxidants dramatically. This counterintuitive phenomenon relies on a substantially different reaction mechanism from that in the absence of an acid: rate‐determining electron transfer occurs from the hydrogen‐bonded phenol to the hydroperoxide cation radical present in equilibrium with the peroxyl radical under these conditions (see scheme).
Bibliography:http://dx.doi.org/10.1002/anie.200903360
ArticleID:ANIE200903360
Ontario MRI
MIUR (Rome)
ark:/67375/WNG-3WFZLLM7-7
istex:F346105B02E6B31FDB9BA002702F86F2B052B7B2
University of Bologna
Canada Research Chairs program
Grants from the University of Bologna, MIUR (Rome), NSERC Canada, Ontario MRI, and the Canada Research Chairs program are gratefully acknowledged.
NSERC Canada
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200903360