title: Reactivity indices profile: a companion tool of the potential energy surface for the analysis of reaction mechanisms. Nucleophilic aromatic substitution reactions as test case.
abstract: We herein report on the usefulness of the reactivity indices profiles along a reaction coordinate. The model is tested to fully describe the reaction mechanism of the title reactions. Group nucleophilicity and electrophilicity profiles help describe the bond-breaking/bond-formation processes and the intramolecular electron density reorganization. The reactivity indices' profile analysis is consistently complemented with hydrogen bonding (HB) effects along the reaction coordinate: the final outcome of the reaction is determined by the stage at which the HB complex can be formed. Transition-state structures located for six reactions studied, including the charged nucleophile thiocyanate, show that the main stabilizing interaction is that formed between the hydrogen atom of the nucleophile and the o-NO(2) group. This result discards the role of HB interaction between the nucleophile and the leaving group previously proposed in the literature.
authors.affiliation: Departamento de Química, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago, Chile. rormazabalt@u.uchile.cl
authors.forename: Rodrigo
authors.initials: R
authors.lastname: Ormazábal-Toledo
authors.forename: Renato
authors.initials: R
authors.lastname: Contreras
authors.forename: Paola R
authors.initials: PR
authors.lastname: Campodónico