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Substituent effects on O-H bond dissociation enthalpies: a computational study.

Authors
  • Wiberg, Kenneth B
  • Ellison, G Barney
  • McBride, J Michael
  • Petersson, George A
Type
Published Article
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society
Publication Date
Jan 10, 2013
Volume
117
Issue
1
Pages
213–218
Identifiers
DOI: 10.1021/jp310510y
PMID: 23206233
Source
Medline
License
Unknown

Abstract

Bond dissociation enthalpies (BDEs) can exhibit dramatic variations resulting from substituent effects. The remarkable range of experimental OH bond dissociation enthalpies have been reproduced using CBS-APNO calculations with very good accuracy, so we have employed these calculations to extend the available BDE data. The effect on these BDEs of lone pairs on the atom adjacent to oxygen shows that conjugation in the product radicals is the most important interaction leading to the wide range of values. The BDE's were found to be linearly related to both the spin density at the radical center and to the change in X-O bond order in going from X-O-H to X-O·.

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