在化复合体中的Si-H激活 - - 一个机械学和理论研究
1Institut für Anorganische und Angewandte Chemie, Fachbereich Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
Journal of the American Chemical Society
|February 26, 2013
概括
这项研究揭示了复合物如何激活中-键,形成胺复合物. 动力学和DFT研究表明,通过两种途径直接添加到化单元.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 催化剂是一种催化剂.
背景情况:
- - (Si-H) 键激活在有机化学中至关重要.
- 复合物是各种键激活的有效催化剂.
- 终端化联体在过渡金属复合体中具有独特的反应性.
研究的目的:
- 调查Si-H键激活的机制,通过一个方形平面的二胺-二复合物与终端化物单元.
- 为了表征由此产生的西胺复合物.
- 阐明控制Si-H激活过程的电子因素.
主要方法:
- 合成和X射线晶体学的酸胺复合物.
- 结合的实验动力学研究.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 三甲基和三甲基西兰的Si-H激活产生了具有良好的特征的胺化合物复合物.
- 将Si-H键直接添加到化单位是拟议的机制.
- 确定了两种独立的反应途径,其中有一种两性化单元.
- 哈梅特研究探讨了电子对过渡状态倾向的影响.
- 对H-H和C-H激活的障碍物进行了比较分析.
结论:
- 化复合物通过直接添加机制促进Si-H键的激活.
- 化物单元表现出两性特征,支持多个反应途径.
- 了解这些通路可以了解催化C-H和H-H激活.
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