Reactivity indices profile: a companion tool of the potential energy surface for the analysis of reaction mechanisms. Nucleophilic aromatic substitution reactions as test case

Date

2013

Type:

Artículo

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7

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Journal Title

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Volume Title

Publisher

American Chemical Society

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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-NO2 group. This result discards the role of HB interaction between the nucleophile and the leaving group previously proposed in the literature.

Description

Centro de Química Médica

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Citation

The Journal of Organic Chemistry, 2013, 78 (3):1091–1097

Keywords

Reactivity Indices, hydrogen bonding, reaction coordinate

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