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Interplay between aromaticity and strain in double group transfer reactions to 1,2‐benzyne
Author(s) -
Fernández Israel,
Cossío Fernando P.
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.24317
Subject(s) - aromaticity , aryne , chemistry , acetylene , moiety , computational chemistry , density functional theory , reactivity (psychology) , valence (chemistry) , valence bond theory , transition state , ring strain , hydrogen atom , molecule , group (periodic table) , molecular orbital , stereochemistry , organic chemistry , medicine , alternative medicine , pathology , catalysis
Density Functional Theory calculations are used to explore the double hydrogen atom transfer from different alkanes to 1,2‐benzyne. State‐of‐the‐art calculations including the Activation Strain Model of reactivity, Energy Decomposition Analysis, and Valence Bond methods, reveal the origins of the relatively low activation barriers computed for these processes compared to the analogous reaction involving acetylene. In addition, the interplay between the in‐plane aromaticity of the corresponding transition states and the variation of the π‐aromaticity associated with the benzyne moiety as well as their influence on the barrier heights of the transformations are analyzed in detail. © 2016 Wiley Periodicals, Inc.