内分子复合体的"违法"双极结合阳离子
Valery F Sidorkin1, Elena F Belogolova1, Evgeniya P Doronina1
1A. E. Favorsky Irkutsk Institute of Chemistry , Siberian Branch of the Russian Academy of Sciences Favorsky, 1 , Irkutsk 664033 , Russian Federation.
Journal of the American Chemical Society
|January 4, 2020
概括
这项研究揭示了双极结合 (DB) 电子导致西拉坦分子中异常的Si-N结合缩短. 这种结构变化取决于二极子时刻和分子几何, 不仅仅是电子脱离能量.
科学领域:
- 计算化学
- 量子化学
- 分子结构和动力学
背景情况:
- 西拉是各种化学领域的潜在应用的子化合物.
- 双极结合 (DB) 离子是过量电子被分子的双极时刻弱结合的物种.
- 了解电子与分子结构的相互作用对于预测化学行为至关重要.
研究的目的:
- 研究双极结合电子对锡拉分子 (XSi(OCH2CH2) 3N) 的结构的影响.
- 探索由西拉衍生的DB离子的形成和结构重组的因素.
- 将计算结果与西拉DB离子的实验数据进行比较.
主要方法:
- 高精度合集群计算,特别是CCSD和CCSD (T) 方法.
- 使用RET-PES进行实验测量.
- 分析分子几何,双极时刻和电子脱离能量.
主要成果:
- 观察到从西拉中形成DB离子时的内核Si·N距离异常缩短.
- 对X=Cl的记录缩短为0.15 Å,超过以前已知的DB离子.
- DB离子形成受双极时刻大小和N(CH2) 3部分的金字塔性影响.
结论:
- 西拉对过多的电子附着的结构反应是独一无二的和复杂的.
- 结构重组的程度取决于Si-N键缩短时的二极矩增加率.
- 这些发现适用于广泛的替代5-azabicyclo[3.3.3]undecanes.
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