The preferred geometry of hydroperoxides is the result of an interplay between electrostatic and hyperconjugative
Marco A S Afonso1, Rodrigo A Cormanich
1University of Campinas, Institute of Chemistry, Department of Organic Chemistry, 13083-970, Campinas, SP, Brazil. cormanich@unicamp.br.
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 nO → 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.
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