A theoretical study of the abstraction reactions of hydroxyl radicals with halogenated aldehydes

Abstract

The semi-empirical quantum mechanical molecular orbital method PM3 has been used to investigate the nature of the transition states for the reactions of hydroxyl radicals with halogenated aldehydes. For each reaction, the geometric and electronic structures of the transition state corresponding to the abstraction of the aldehydic hydrogen atom were determined. The results indicate that the transition states are reactant-like and, from the calculation of electronic charge distributions, it can be concluded that changes in the reactivity along the series are mainly due to inductive effects in the transition states.