Ned Porter
Faculty Member
Last active: 5/29/2014

Role of hyperconjugation in determining carbon-oxygen bond dissociation enthalpies in alkylperoxyl radicals.

Pratt DA, Porter NA
Org Lett. 2003 5 (4): 387-90

PMID: 12583725 · DOI:10.1021/ol027094x

[reaction: see text] Theoretical calculations of carbon-oxygen bond dissociation enthalpies in substituted methylperoxyl radicals (YCH(2)OO*) reveal that bond strengths are not governed solely by the stability of YCH2* radicals but are largely affected by hyperconjugation when Y is electron-donating or conjugating. In many cases, this hyperconjugative effect is greater than stabilization of the methyl radical by Y. All electron-withdrawing Y exert small destabilizing effects via inductive withdrawal of electrons from the polarized C-OO* bond.

MeSH Terms (4)

Free Radicals Models, Molecular Peroxides Thermodynamics

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