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Solvent and Autocatalytic Effects on the Stabilisation of the σ‐Complex during Electrophilic Aromatic Chlorination
Author(s) -
Van Lommel Ruben,
Moors Samuel L. C.,
De Proft Frank
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800385
Subject(s) - metadynamics , chemistry , acetonitrile , computational chemistry , solvent effects , electrophile , autocatalysis , solvent , acetic acid , solvation , reaction mechanism , catalysis , organic chemistry , photochemistry , molecular dynamics
The solvent and autocatalytic effects of the electrophilic aromatic chlorination of benzene are studied using a combined approach of static calculations and ab initio metadynamics simulations. Different possible reaction pathways are investigated and the influence of the solvents (CCl 4 , acetonitrile and acetic acid) is thoroughly assessed. Our results show that the stability and lifetime of a charged σ‐complex is increased by electrostatic stabilisation effects of the environment, which can originate from catalytic HCl, solvating effects of polar solvents (acetonitrile), or specific hydrogen bonding interactions with the solvent (acetic acid). Metadynamics simulations reveal a new chlorine addition mechanism explaining the autocatalytic effects of the reaction. The strength of combining static calculations and metadynamics simulations is highlighted, which provide complementary insight into chemical reactions in solvent.