title: Competitive substituent effects on the reactivity of aromatic rings.
abstract: We performed second order perturbation theory calculations of gas phase proton affinities for o, m, p-nitroaniline at all positions and attempted correlations of the thermodynamic stability of the products with several reactivity indices: inductive effects from resonance, partial charges, and frontier orbital related indices such as local nucleophilic and electron-donating powers, global hardness of the products, and the substituent push-pull effect. All protonation reactions at ring positions are predicted to be exothermic. Resonance and charge analysis give inconsistent correlations with proton affinities, while the condensed nucleophilic Fukui function, electron-donating power, global hardness, and push-pull effect show promising trends.
authors.affiliation: Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, AA 1226 Medellín, Colombia.
authors.forename: Cinthia
authors.initials: C
authors.lastname: Jaramillo
authors.forename: Doris
authors.initials: D
authors.lastname: Guerra
authors.forename: Luis Fernando
authors.initials: LF
authors.lastname: Moreno
authors.forename: Albeiro
authors.initials: A
authors.lastname: Restrepo