title: DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes.
abstract: 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.
authors.affiliation: Tomsk Polytechnic University, 634050 Tomsk, Russia.
authors.forename: Victor D
authors.initials: VD
authors.lastname: Filimonov
authors.forename: Oleg Kh
authors.initials: OKh
authors.lastname: Poleshchuk
authors.forename: Elena A
authors.initials: EA
authors.lastname: Krasnokutskaya
authors.forename: Gernot
authors.initials: G
authors.lastname: Frenking
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D002236:Carbohydrate Conformation; D054879:Halogenation; D008958:Models, Molecular; D013816:Thermodynamics
chemical_list: D001555:Benzene Derivatives