Wheland Intermediates: An ab Initio Valence Bond Study

Mélodie Hadzic (1) , Benoît Braïda (1) , François Volatron (1)

1 LCT - Laboratoire de chimie théorique

The traditional resonance model for electrophilic attacks on substituted aromatic rings is revisited using high level valence bond (VB) calculations. A large π-donation is found in the X = NH2 case and a weaker one for the X = Cl case, not only for ortho and para isomers but also for the meta case, which can be explained by considering five (not three) fundamental VB structures. No substantial π-effect is found in the X = NO2 case, generally viewed as π-attractive.

Domaines: Chimie théorique et/ou physique

Mélodie Hadzic, Benoît Braïda, François Volatron. Wheland Intermediates: An ab Initio Valence Bond Study. Organic Letters, 2011, 13 (8), pp.1960-1963. ⟨10.1021/ol200327s⟩. ⟨hal-01627703⟩