The preferred geometry of hydroperoxides is the result of an interplay between electrostatic and hyperconjugative effects

Abstract

Steric, electrostatic and hyperconjugative effects were evaluated in the natural bond orbital framework as candidate sources of the preferred geometry of hydroperoxides. Stabilising 1,2-^δ+H–^δ−O electrostatic interactions and n_O → σ*_OR hyperconjugative interactions were found to be the driving force for the preferred anticlinal or perpendicular geometries, respectively. There is an interesting interplay between these two effects: when one increases, the other decreases. On the other hand, steric effects showed negligible contributions to the conformational behaviour of the studied molecules. Also, HO–OR bond dissociation energy appeared to be dependent on RO˙ radical stability, which is governed by hyperconjugation.