Facile heterolytic bond splitting of molecular chlorine upon reactions with Lewis bases: Comparison with ICl and I2

IF 3.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Computational Chemistry Pub Date : 2024-09-23 DOI:10.1002/jcc.27507

Anna V. Pomogaeva, Anna S. Lisovenko, Alexey Y. Timoshkin

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Abstract

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.

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分子氯与路易斯碱反应时容易发生异解键分裂：与 ICl 和 I2 的比较

在 M06-2X/def2-TZVPD、CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz 理论水平下，对分子 Cl2 与含氮路易斯碱 (LB) 反应时分子配合物的形成及随后卤素-卤素键的异解分裂进行了计算研究。获得的结果与 ICl 和 I2 分子的数据进行了比较。反应路径表明，在 Cl2∙LB 复合物中，异解 Cl-Cl 键分裂的活化能低于 Cl2 分子同解分裂成氯自由基的活化能。在气相中，X2∙Py 分子络合物的异解卤素分裂形成[XPy2]+......接触离子对，在 Cl2 和 I2 的情况下是轻微的内热，而在 ICl 的情况下则是轻微的放热。{[ClPy2]+...}2二聚体的形成使整个过程放热。考虑到极性溶剂有利于离子物种的生成，在路易斯碱存在的情况下生成供体稳定的 Cl+ 预期是有利的。因此，在极性溶剂中，通过供体稳定的 Cl+ 物种进行氧化的途径是同解 Cl-Cl 键断裂的可行替代方法。

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来源期刊

Journal of Computational Chemistry 化学-化学综合

CiteScore

6.60

自引率

3.30%

发文量

247

审稿时长

1.7 months

期刊介绍： This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.