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Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials
Author(s) -
Fievez Tim,
Pinter Balazs,
Geerlings Paul,
Bickelhaupt F. Matthias,
De Proft Frank
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201001318
Subject(s) - hsab theory , regioselectivity , chemistry , electrophile , computational chemistry , interaction energy , electrophilic aromatic substitution , interaction model , electrophilic addition , electrophilic substitution , substitution reaction , benzene , molecular orbital , stereochemistry , organic chemistry , molecule , psychology , pedagogy , catalysis
The S E Ar reaction was scrutinized using a quantitative, fragment‐based interaction energy decomposition analysis (EDA) as implemented in the ADF program. The interaction energy between monosubstituted benzene derivatives and a model electrophile at the onset of the reaction was studied and decomposed into Pauli repulsion, electrostatic interaction and orbital interaction terms for a plane parallel to the molecular plane. As such experimentally observed selectivity patterns arise in the orbital interaction, stressing again the role of both electrophile and benzene derivative in determining the regioselectivity. Using the HSAB principle and MO theory, the orientation mechanism of the SEAr is further explored.