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Revisiting the concept of the (a)synchronicity of diels‐alder reactions based on the dynamics of quasiclassical trajectories
Author(s) -
de Souza Miguel A. F.,
Ventura Elizete,
do Monte Silmar A.,
Riveros José M.,
Longo Ricardo L.
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24245
Subject(s) - synchronicity , cyclopentadiene , concerted reaction , computational chemistry , chemistry , cycloaddition , character (mathematics) , dynamics (music) , mechanism (biology) , physics , mathematics , organic chemistry , quantum mechanics , catalysis , philosophy , geometry , epistemology , acoustics
A number of model Diels‐Alder (D‐A) cycloaddition reactions (H 2 CCH 2 + cyclopentadiene and H 2 CCHX + 1,3‐butadiene, with X = H, F, CH 3 , OH, CN, NH 2 , and NO) were studied by static (transition state ‐ TS and IRC) and dynamics (quasiclassical trajectories) approaches to establish the (a)synchronous character of the concerted mechanism. The use of static criteria, such as the asymmetry of the TS geometry, for classifying and quantifying the (a)synchronicity of the concerted D‐A reaction mechanism is shown to be severely limited and to provide contradictory results and conclusions when compared to the dynamics approach. The time elapsed between the events is shown to be a more reliable and unbiased criterion and all the studied D‐A reactions, except for the case of H 2 CCHNO, are classified as synchronous, despite the gradual and quite distinct degrees of (a)symmetry of the TS structures. © 2015 Wiley Periodicals, Inc.