Reactions of peroxy radicals with hydrocarbons and alcohols: Transition state geometry and the polar effect

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The reaction EtOO• + EtH → EtOOH + Et• was studied by the intersecting parabolas method and calculated using density functional theory. The interatomic C–H, O–H, and C–O distances of the transition state for this reaction were calculated using these methods. The formulas for calculating these distances from experimental data were obtained. Similar calculations and comparisons were carried out for the reaction EtOO• + MeCH2OH → EtOOH + MeC•HOH. The polar effect of the hydroxy groups on the transition state manifested itself in a decrease in the activation energy and in the formation of a nonlinear structure of the transition state. An empirical formula for estimating the C–H–O angle in the transition state from the enthalpy and activation energy was derived.