化键捐赠者对易斯基的亲缘关系在溶液中:一个关键的实验理论联合研究
Loïc Groslambert1, Yann Cornaton2, Matej Ditte3
1LASYROC, UMR 7177 CNRS, University of Strasbourg, 1 Rue Blaise Pascal, F-67000, Strasbourg, France.
Chemistry (Weinheim an der Bergstrasse, Germany)
|November 16, 2023
概括
泰鲁盐表现出易斯酸性,与易斯基形成复合物,如OPPh3.3. 它们的结合亲和力受盐结构和溶剂的影响,库伦比克和分散力是关键驱动因素.
科学领域:
- 有机金属化学 有机金属化学
- 超分子化学 超分子化学
- 计算化学计算化学
背景情况:
- 泰鲁盐是具有潜在的易斯酸性质的有机硫化合物.
- 了解它们与易斯基的相互作用对于开发新的催化和材料应用至关重要.
研究的目的:
- 为了合成和表征盐.
- 为了研究它们的易斯酸性质和易斯基溶液中的复杂形成.
- 用实验和理论方法阐明这些相互作用背后的驱动力.
主要方法:
- 盐的合成和X射线衍射分析.
- 使用扩散排序NMR光谱 (DOSY) 和异热定位热量计 (ITC) 的溶液相研究.
- 高层次的DFT和ab-initio计算,包括DFT-D4/MBD-vdW方法.
主要成果:
- 21个盐的结构特征,显示电友Te中心.
- 泰鲁可以结合多达三个OPPH3分子,结合度从-0.5到-5kcal/mol不等.
- 库伦比和分散相互作用,以及效应,主导复杂形成,而轨道相互作用不那么重要.
结论:
- 泰鲁盐是有效的易斯酸,能够与易斯基形成稳定的复合物.
- 替代子和对子的电子特性显著影响结合热力学.
- MBD-vdW方法提供了与实验数据更好的一致性,用于预测更高阶复合体的热力学.
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