Variable trends in R-X bond dissociation energies (R = Me, Et, i-Pr, t-Bu)

Michelle L Coote; Addy Pross; Leo Radom

doi:10.1021/ol035860+

Variable trends in R-X bond dissociation energies (R = Me, Et, i-Pr, t-Bu)

Org Lett. 2003 Nov 27;5(24):4689-92. doi: 10.1021/ol035860+.

Authors

Michelle L Coote¹, Addy Pross, Leo Radom

Affiliation

¹ Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia. mcoote@rsc.anu.edu.au

PMID: 14627416
DOI: 10.1021/ol035860+

Abstract

[structure: see text] High level ab initio molecular orbital calculations confirm experimental indications that the effect of alkyl substituents (R = Me, Et, i-Pr, t-Bu) on R-X bond dissociation energies varies considerably according to the nature of X. A simple qualitative explanation in terms of valence-bond theory is presented, highlighting the increasing importance of the stabilization of R-X by the ionic R(+)X(-) configuration for electronegative X substituents (such as F, OH, and OCH(3)).