碳氧键裂解与eta9,eta5-bis(indenyl) 三明治复合体的碳氧键裂解
Christopher A Bradley1, Luis F Veiros, Doris Pun
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
Journal of the American Chemical Society
|December 21, 2006
概括
双 () 复合物很容易在基乙烯中切割C-O键,形成氧化物复合物. 这种反应机制涉及决定速率的C-H激活和随后的β-氧化物消除.
科学领域:
- 有机金属化学 有机金属化学
- 化学化学 化学
- 催化剂是一种催化剂.
背景情况:
- 双 () 复合物是多用途的有机金属化合物.
- 了解它们与以太的反应性对于合成应用至关重要.
研究的目的:
- 为了研究 bis(indenyl) zirconium 复合物与dialkyl 以太的反应机制.
- 为了阐明氧化化合物复合物和自由烯的形成.
主要方法:
- 处理eta9,eta5-bis(indenyl) 复合物与各种基乙烯的处理.
- 动态同位素效应研究和速率分析.
- 热解eta6,eta5-bis(indenyl) THF化合物. 热解
- 机械学和计算研究.
主要成果:
- 容易发生C-O键裂变,产生eta5,eta5-bis(indenyl) 氧化化合物复合物和烯酸.
- 在乙烯形成时分离出一种罕见的,结晶学特征的,没有基的eta5,eta5-bis(indenyl) 基乙烯复合物.
- 证据支持一种涉及速度决定性C-H激活的机制,其次是β-氧化物消除.
- 乙6,乙5-bis的热解也导致了C-O键裂变.
结论:
- 反应通过一种机制进行,涉及触旋转基重组,C-H激活和C-O键裂变.
- 这项研究提供了与乙相关的双 () 复合物的反应性,这些复合物对于有机金属合成和催化有意义.
相关概念视频
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