Format

Send to:

Choose Destination
See comment in PubMed Commons below
J Phys Chem A. 2013 Jan 10;117(1):213-8. doi: 10.1021/jp310510y. Epub 2012 Dec 17.

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

Author information

  • 1Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA. kenneth.wiberg@yale.edu

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·.

PMID:
23206233
[PubMed]
PubMed Commons home

PubMed Commons

0 comments
How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Write to the Help Desk