氨基胺催化溶剂C-H键激活作为cationic十甲基齐尔科诺olefin聚合催化剂的失活路径
Itzel Guerrero Rios1, Elena Novarino, Siebe van der Veer
1Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Journal of the American Chemical Society
|November 6, 2009
概括
三级氨基通过西格玛键转化加速甲-d(5) 的C-D激活. 这涉及初始去质子化和随后与试基离子发生反应,形成西格玛-烯复合体.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- 十甲基齐尔科诺复合物是活性催化剂.
- C-H和C-D激活是有机金属化学中的基本反应.
研究的目的:
- 研究三级氨基在由十甲基齐尔科诺森甲基离子体催化的甲-d(5) 的C-D激活中的作用.
- 为了阐明加速的西格玛键转化反应的机制.
主要方法:
- 实验研究C-D激活使用甲-d(5) 和十甲基齐尔科诺甲基离子前体.
- 计算研究 (DFT) 用于调查反应机制.
主要成果:
- 三级氨基显著加快甲-d的C-D激活.
- 计算研究表明,一种机制涉及金属的协调球体内的氨基的初始deprotonation.
- 反应通过西格玛键转化进行,形成西格玛-阿里尔复合物.
结论:
- 三级氨基作为催化剂或促进剂,通过十甲基基烯复合体的甲-d(5) 的西格玛键转化.
- 拟议的机制提供了对氨酸加速的C-H/C-D激活反应的洞察力.
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