Role of hyperconjugation in determining carbon-oxygen bond dissociation enthalpies in alkylperoxyl radicals |
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Authors: | Pratt Derek A Porter Ned A |
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Institution: | Department of Chemistry and Center for Molecular Toxicology, Vanderbilt University, Nashville, Tennessee 37235, USA. |
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Abstract: | 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. |
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