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Pathways of electrophilic aromatic substitution reactions catalyzed by group 13 trihalides: An ab initio study
Author(s) -
Volkov Alexey N.,
Timoshkin Alexey Y.,
Suvorov Andrew V.
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20420
Subject(s) - chemistry , halide , ab initio , electrophile , computational chemistry , catalysis , stoichiometry , electrophilic substitution , transition metal , ab initio quantum chemistry methods , main group element , transition state , metal halides , medicinal chemistry , organic chemistry , molecule
An ab initio study of the two possible pathways of ectrophilic aromatic substitution reaction catalyzed by monomeric and dimeric forms of group 13 metal halides has been performed. Optimized geometries of π, σ‐complexes and corresponding transition states have been obtained at second‐order Møller–Plesset/ LANL2DZ(d)+ level of theory. It is found that operation of the dimeric pathway is more favorable both thermodynamically and kinetically. Thus, it is expected that catalytical activity of the metal halide will be greatly increased if the stoichiometric ratio 2:1 is employed. Obtained results are in qualitative agreement with available experimental data. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005