Understanding Reaction Mechanisms in Organic Chemistry from Catastrophe Theory Applied to the Electron Localization Function Topology

Thomʼs catastrophe theory applied to the evolution of the topology of the electron localization function (ELF) gradient field constitutes a way to rationalize the reorganization of electron pairing and a powerful tool for the unambiguous determination of the molecular mechanisms of a given chemical...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2008-08, Vol.112 (31), p.7128-7136
Main Authors: Polo, Victor, Andres, Juan, Berski, Slawomir, Domingo, Luis R, Silvi, Bernard
Format: Article
Language:English
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Summary:Thomʼs catastrophe theory applied to the evolution of the topology of the electron localization function (ELF) gradient field constitutes a way to rationalize the reorganization of electron pairing and a powerful tool for the unambiguous determination of the molecular mechanisms of a given chemical reaction. The identification of the turning points connecting the ELF structural stability domains along the reaction pathway allows a rigorous characterization of the sequence of electron pair rearrangements taking place during a chemical transformation, such as multiple bond forming/breaking processes, ring closure processes, creation/annihilation of lone pairs, transformations of C−C multiple bonds into single ones. The reaction mechanism of some relevant organic reactions: Diels−Alder, 1,3-dipolar cycloaddition and Cope rearrangement are reviewed to illustrate the potential of the present approach.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp801429m