Hydrogen Abstraction by Alkoxyl Radicals: Computational Studies of Thermodynamic and Polarity Effects on Reactivities and Selectivities

Density functional theory calculations (ωB97X-D) are reported for the reactions of methoxy, tert-butoxy, trichloroethoxy, and trifluoroethoxy radicals with a series of 26 C–H bonds in different environments characteristic of a variety of hydrocarbons and substituted derivatives. The variations in activation barriers are analyzed with modified Evans–Polanyi treatments to account for polarity and unsaturation effects. The treatments by Roberts and Steel and by Mayer have inspired the development of a simple treatment involving the thermodynamics of reactions, the difference between the reactant radical and product radical electronegativities, and the absence or presence of α-unsaturation. The three-parameter equation (ΔH ⧧ = 0.52ΔH rxn(1 – d) – 0.35ΔχAB 2 + 10.0, where d = 0.44 when there is α-unsaturation to the reacting C–H bond), correlates well with quantum mechanically computed barriers and shows the quantitative importance of the thermodynamics of reactions (dictated by the reactant and the product bond dissociation energies) and polar effects.