title: Origin of the Regioselectivity in the Gas-Phase Aniline+CH3 (+) Electrophilic Aromatic Substitution.
abstract: Nonadiabatic ab initio molecular dynamics simulations are carried out to monitor the attack of CH3 (+) 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.
authors.affiliation: Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090 Vienna (Austria).
authors.forename: Daniel
authors.initials: D
authors.lastname: Kinzel
authors.affiliation: Institute of Chemistry and the Lise-Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, Jerusalem (Israel).
authors.forename: Shmuel
authors.initials: S
authors.lastname: Zilberg
authors.affiliation: Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090 Vienna (Austria). leticia.gonzalez@univie.ac.at.
authors.forename: Leticia
authors.initials: L
authors.lastname: González
keywords: ab initio calculations; aromatic substitution; electrophilic substitution; molecular dynamics; regioselectivity