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Formation of molecular complexes and subsequent heterolytic halogen-halogen bond splitting upon reactions of molecular Cl2 with nitrogen-containing Lewis bases (LB) are computationally studied at M06-2X/def2-TZVPD and for selected compounds at CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz levels of theory. Obtained results are compared with data for ICl and I2 molecules. Reaction pathways indicate, that in case of Cl2∙LB complexes the activation energies for the heterolytic Cl-Cl bond splitting are lower than the activation energies of the homolytic splitting of Cl2 molecule into chlorine radicals. The heterolytic halogen splitting of molecular complexes of X2∙Py with formation of [XPy2]+ contact ion pairs in the gas phase is slightly endothermic in case of Cl2 and I2, but slightly exothermic in the case of ICl. Formation of {[ClPy2]+}2 dimers makes the overall process exothermic. Taking into account that polar solvents favor ionic species, generation of donor-stabilized Cl+ in the presence of the Lewis bases is expected to be favorable. Thus, in polar solvents the oxidation pathway via donor-stabilized Cl+ species is viable alternative to the homolytic Cl-Cl bond breaking.
Язык оригиналаанглийский
Номер статьиe27507
Число страниц11
ЖурналJournal of Computational Chemistry
Том46
Номер выпуска1
Дата раннего онлайн-доступа23 сен 2024
DOI
СостояниеОпубликовано - 5 янв 2025

    Предметные области Scopus

  • Химия (все)

    Области исследований

  • chemical bond, chlorine, heterolytic bond splitting, isomers, Lewis bases, molecular complexes

ID: 124960554