Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 7044-7050 |
| Number of pages | 7 |
| Journal | Chemistry - a European Journal |
| Volume | 24 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - 11 May 2018 |
Keywords
- Wheland σ-complex
- aromatic chlorination
- electrophilic aromatic substitution
- metadynamics
- reaction mechanism