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Origin of the Regioselectivity in the Gas‐Phase Aniline+CH 3 + Electrophilic Aromatic Substitution
Author(s) -
Kinzel Daniel,
Zilberg Shmuel,
González Leticia
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500256
Subject(s) - electrophilic aromatic substitution , chemistry , regioselectivity , aniline , electrophilic substitution , electrophile , substitution reaction , ab initio , ab initio quantum chemistry methods , computational chemistry , conical intersection , nucleophilic aromatic substitution , aromaticity , nucleophilic substitution , molecule , organic chemistry , catalysis
Nonadiabatic ab initio molecular dynamics simulations are carried out to monitor the attack of CH 3 + on aniline in the gas phase to form the corresponding σ complexes. The reaction is ultrafast and is governed by a single electron transfer within 30 fs, which involves two sequential conical intersections and finally produces a radical pair. Positive‐charge allocation in the aromatic compound is found to govern the substitution pattern in ortho , meta , or para position. Although the major products in the first step of the electrophilic aromatic substitution are the ortho and para σ complexes, initially 26 % of the simulated trajectories also form meta complexes, which then undergo H shifts, mainly to the para position.