DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes

Victor D. Filimonov, Oleg Kh Poleshchuk, Elena A. Krasnokutskaya, Gernot Frenking

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13 Citations (Scopus)


Quantum chemical calculations at the B3LYP/6-311G*level have been carried out in order to investigate the reaction mechanisms of the iodination of benzene and its monosubstituted derivatives with ICl, I +, I 3 + and reagents containing N-I and O-I bonds as the iodinating agents. The results are compared with those obtained for chlorination by Cl + and Cl 2, both in the gas phase and in methanol solution using the PCM solvent model. We have also used the MP2/DGDZVP level of theory and the IEFPCM model to perform comparisons in a few cases. The thermodynamic parameters for the reactions have been calculated, the structures of the intermediate products (π- and σ-complexes) and transition states have been optimized, and the profiles of the free energy surfaces have been constructed.

Original languageEnglish
Pages (from-to)2759-2771
Number of pages13
JournalJournal of Molecular Modeling
Issue number11
Publication statusPublished - Nov 2011



  • π-Complex
  • σ-Complex transition state
  • Chlorination
  • DFT
  • Iodination

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications
  • Computational Theory and Mathematics
  • Catalysis
  • Organic Chemistry
  • Inorganic Chemistry

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