In the framework of SMD approach a systematic computational study of structural, electronic and thermodynamic properties of molecular complexes of Cl2, ICl and I2 with series of N‐containing Lewis bases in solvents of different polarity was carried out. Results indicate that molecular complexes of Cl2 with strong and medium‐strong LB undergo spontaneous ionization in the acetonitrile solution. The increase of the solvent polarity can change the nature of interaction in X'XLB systems from molecular X'X ← LB donor‐acceptor complexes to 3‐center 4‐electron bound X'→X+ ← LB in solvents of medium polarity and to the contact ion pairs X'→[XLB]+ in polar solvents. Thus, the controlled generation of cationic [LB∙X]+ species is possible by varying the nature of LB, varying the nature of the solvent, and varying the nature of the halogen X. Molecular Cl2 has the greatest tendency to form ionic species in polar solvents. Spontaneous ionization of molecular nσ complexes of chlorine with strong LB in medium‐polar solvents (starting from OEt2, ε = 4.24) should not be neglected and single point solvation energy computations on gas phase optimized geometries are not reliable for such systems.

中文翻译：

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溶剂化对双原子卤素与含氮供体分子复合物键合的影响及其在异质溶解卤素-卤素键分裂方面的稳定性


在 SMD 方法的框架内，对 Cl2、ICl 和 I2 的分子复合物的结构、电子和热力学性质进行了系统的计算研究，这些复合物具有不同极性的溶剂中的一系列含 N 路易斯碱。结果表明，Cl2 与强 LB 和中强 LB 的分子复合物在乙腈溶液中发生自发电离。溶剂极性的增加可以改变 X'XLB 系统中的相互作用性质，从分子 X'X ← LB 供体-受体复合物转变为中等极性溶剂中的 3 中心 4 电子结合 X'→X+ ← LB，以及极性溶剂中的接触离子对 X'→[XLB]+。因此，通过改变 LB 的性质、改变溶剂的性质和改变卤素 X 的性质，可以控制阳离子 [LB∙X]+ 物质的产生。分子 Cl2 在极性溶剂中形成离子物质的倾向最大。在中等极性溶剂（从 OEt2 开始，ε = 4.24）中，氯与强 LB 的分子 nσ 络合物的自发电离不应被忽视，并且气相优化几何形状上的单点溶剂化能量计算对于此类系统并不可靠。