Artículos de revistas
Reactivity Indices Profile: A Companion Tool of the Potential Energy Surface for the Analysis of Reaction Mechanisms. Nucleophilic Aromatic Substitution Reactions as Test Case
Fecha
2013Registro en:
J. Org. Chem. 2013, 78, 1091−1097
dx.doi.org/10.1021/jo3025048
Autor
Ormazábal Toledo, Rodrigo
Contreras Ramos, Renato
Campodónico, Paola R.
Institución
Resumen
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-NO2 group. This result discards the
role of HB interaction between the nucleophile and the leaving group
previously proposed in the literature.