Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids

Derek A. Pratt, Jeremy H. Mills, Ned A. Porter

Research output: Contribution to journalArticlepeer-review

138 Scopus citations

Abstract

Theoretical calculations were carried out to provide a framework for understanding the free radical oxidation of unsaturated lipids. The carbon-hydrogen bond dissociation enthalpies (BDEs) of organic model compounds and oxidizable lipids (R-H) and the carbon-oxygen bond dissociation enthalpies of peroxyl radical intermediates (R-OO.) have been calculated. The carbon-hydrogen BDEs correlate with the rate constant for propagation of free radical autoxidation, and the carbon-oxygen BDEs of peroxyl radicals correlate with rate constants for β-fragmentation of these intermediates. Oxygen addition to intermediate carbon radicals apparently occurs preferentially at centers having the highest spin density. The calculated spin distribution therefore provides guidance about the partitioning of oxygen to delocalized carbon radicals. Where the C-H BDEs are a function of the extent of conjugation in the parent lipid and the stability of the carbon radical derived therefrom, C-OO. BDEs are also affected by hyperconjugation. This gives way to different rates of β-fragmentation of peroxyl radicals formed from oxygen addition at different sites along the same delocalized radical. We have also studied by both theory and experiment the propensity for benzylic radicals to undergo oxygen addition at their ortho and para carbons which, combined, possess an equivalent unpaired electron spin density as the benzylic position itself. We find that the intermediate peroxyl radicals in these cases have negative C-OO. BDEs and, thus, have rate constants β-fragmentation that exceed the diffusion-controlled limit for the reaction of a carbon-centered radical with oxygen.

Original languageEnglish (US)
Pages (from-to)5801-5810
Number of pages10
JournalJournal of the American Chemical Society
Volume125
Issue number19
DOIs
StatePublished - May 14 2003
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids'. Together they form a unique fingerprint.

Cite this