离子的分子内素稳定性指导了轮动力学
Paola Romanato1, Simon Duttwyler, Anthony Linden
1Organic Chemistry Institute, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland.
Journal of the American Chemical Society
|May 27, 2010
概括
这项研究揭示了通过旋转轮机制在基离子中发生动态交换. 这与其类相应物观察到的旋转过程形成鲜明对比,突出显示了素在化学动态中的作用.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
- 反应机制 反应机制
背景情况:
- 五价基具有独特的几何形状和反应性.
- 协调影响了中心的动态行为.
研究的目的:
- 为了阐明2,6-Bis(2,6-difluorophenyl) phenyldimethylsilanium离子中素交换的机制.
- 为了比较和在中心交换的动态过程.
主要方法:
- 分子几何和过渡状态的计算建模.
- 使用立体化学描述器分析动态过程.
主要成果:
- 衍生物 (1a) 采用了三角形-双形几何形状,具有顶协调.
- 的交换通过一个旋转轮机制发生,其过渡状态与C (s) 相称.
- 类型 (1b) 呈现出一个旋转交换机制.
结论:
- 五价酸的动态行为取决于协调素的性质.
- 和之间,素交换的立体化学途径显著不同.
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