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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ORCID:
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