Faculty of Science, Ontario Tech University/UOIT, Oshawa, ON, L1G 0C5, Canada.
Chempluschem. 2020 Nov;85(11):2438-2445. doi: 10.1002/cplu.202000626.
Complexes of a polar molecule (benzene trioxide) and alkali halide diatoms are predicted to form stable conformers through not only a common attachment, but also trapping the molecule between the counterions. Two possible low- and no-barrier routes of formation of such an insertion complex are identified, and stability and other properties of this and other conformers are analyzed, including polarity and charge distribution. Calculated IR spectra indicate a bright feature specific for the insertion complex, facilitating its reliable experimental detection. Isomerization of the ion-pair-trapped molecule shows a nonobvious inhibition effect (through an increased potential energy barrier) compared to the free molecule due to the reduction of its polarity in the isomerization. Formation of a flatter isomer, trioxonine, is clearly "reported" by a sharp alteration of the IR spectrum, distinguishable also from its variation for the nonreactive relaxation of the insertion complex into an attached one.
预测极性分子（三氧化苯）和碱金属卤化物二原子分子通过非共有附着，以及将分子捕获在反离子之间，形成稳定的构象。确定了形成这种插入配合物的两种可能的低能垒和无能垒途径，并分析了这种插入配合物和其他构象的稳定性和其他性质，包括极性和电荷分布。计算的红外光谱表明，对于插入配合物存在一个特定的明亮特征，有利于其可靠的实验检测。与自由分子相比，离子对捕获的分子的异构化显示出非明显的抑制效应（通过增加势能垒），这是由于其在异构化过程中极性降低。平面异构体三氧杂环戊烯的形成通过红外光谱的急剧变化“明显报告”，这也与插入配合物向附着配合物的非反应性弛豫的变化区分开来。
