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Facile heterolytic bond splitting of molecular chlorine upon reactions with Lewis bases: Comparison with ICl and I2. / Помогаева, Анна Владимировна; Лисовенко, Анна Сергеевна; Тимошкин, Алексей Юрьевич.
в: Journal of Computational Chemistry, Том 46, № 1, e27507, 05.01.2025.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Facile heterolytic bond splitting of molecular chlorine upon reactions with Lewis bases: Comparison with ICl and I2
AU - Помогаева, Анна Владимировна
AU - Лисовенко, Анна Сергеевна
AU - Тимошкин, Алексей Юрьевич
PY - 2025/1/5
Y1 - 2025/1/5
N2 - 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.
AB - 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.
KW - chemical bond
KW - chlorine
KW - heterolytic bond splitting
KW - isomers
KW - Lewis bases
KW - molecular complexes
KW - Lewis bases
KW - chemical bond
KW - chlorine
KW - heterolytic bond splitting
KW - isomers
KW - molecular complexes
UR - https://onlinelibrary.wiley.com/doi/10.1002/jcc.27507
UR - https://www.mendeley.com/catalogue/df51510d-24f6-3f28-818c-694b616fea35/
U2 - 10.1002/jcc.27507
DO - 10.1002/jcc.27507
M3 - Article
VL - 46
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 1
M1 - e27507
ER -
ID: 124960554