title: Stability of carbon-centered radicals: effect of functional groups on the energetics of addition of molecular oxygen.
abstract: In this paper we examine a series of hydrocarbons with structural features which cause a weakening of the C-H bond. We use theoretical calculations to explore whether the carbon-centered radicals R(*) which are created after breaking the bond can be stabilized enough so that they resist the addition of molecular oxygen, i.e. where the reaction R(*) + O(2) --> ROO(*) becomes energetically unfavorable. Calculations using a B3LYP-based method provide accurate bond dissociation enthalpies (BDEs) for R-H and R-OO(*) bonds, as well as Gibbs free energy changes for the addition reaction. The data show strong correlations between R-OO(*) and R-H BDEs for a wide variety of structures. They also show an equally strong correlation between the R-OO(*) BDE and the unpaired spin density at the site of addition. Using these data we examine the major functional group categories proposed in several experimental studies, and assess their relative importance. Finally, we combine effects to try to optimize resistance to the addition of molecular oxygen, an important factor in designing carbon-based antioxidants.
authors.affiliation: Department of Chemistry, Carleton University, 1125 Colonel By Drive, Ottawa, Ontario, Canada K1S 5B6. jim_wright@carleton.ca
authors.forename: James S
authors.initials: JS
authors.lastname: Wright
authors.forename: Hooman
authors.initials: H
authors.lastname: Shadnia
authors.forename: Leonid L
authors.initials: LL
authors.lastname: Chepelev
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D015203:Reproducibility of Results; D013816:Thermodynamics
chemical_list: D005609:Free Radicals; D006838:Hydrocarbons; D010100:Oxygen