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

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

Research output: Contribution to journalArticle

133 Citations (Scopus)

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

Fingerprint

Lipids
Enthalpy
Carbon
Oxygen
Rate constants
Free radicals
Free Radicals
Hydrogen
Hydrogen bonds
perhydroxyl radical
Reactive Oxygen Species
Electrons
Oxidation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids. / Pratt, Derek A.; Mills, Jeremy; Porter, Ned A.

In: Journal of the American Chemical Society, Vol. 125, No. 19, 14.05.2003, p. 5801-5810.

Research output: Contribution to journalArticle

@article{f3cca95094c044e6823738c4783e0a40,
title = "Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids",
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.",
author = "Pratt, {Derek A.} and Jeremy Mills and Porter, {Ned A.}",
year = "2003",
month = "5",
day = "14",
doi = "10.1021/ja034182j",
language = "English (US)",
volume = "125",
pages = "5801--5810",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "19",

}

TY - JOUR

T1 - Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids

AU - Pratt, Derek A.

AU - Mills, Jeremy

AU - Porter, Ned A.

PY - 2003/5/14

Y1 - 2003/5/14

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0037620493&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037620493&partnerID=8YFLogxK

U2 - 10.1021/ja034182j

DO - 10.1021/ja034182j

M3 - Article

VL - 125

SP - 5801

EP - 5810

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 19

ER -