Zr(IV) 二复合物的结构和反应性
Fan Wu1, Aswini K Dash, Richard F Jordan
1Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA.
Journal of the American Chemical Society
|November 26, 2004
概括
本研究详细介绍了复合物的合成和反应性. 绝缘阻碍复合体表现出独特的热C-H激活,与光化学反应较少的人群相比,它们具有独特的热C-H激活.
科学领域:
- 有机金属化学 有机金属化学
- 合金复合体 合金复合体
- 协调化学 协调化学
背景情况:
- conocene复合物是多功能催化剂和合成中间体.
- 了解连接体对反应性的影响对于催化剂设计至关重要.
- 二复合物具有独特的反应途径.
研究的目的:
- 为了合成和表征的新型二复合物.
- 研究这些复合物的热和光化学反应性.
- 为了阐明固体质量对反应通路的影响.
主要方法:
- 合成复合物与不同的环二烯连接物.
- 使用光谱技术进行表征 (NMR,X射线晶体学).
- 在二的热和光化学条件下的反应性的研究.
主要成果:
- 甲复合物的合成 [{C5R5) 2ZrR'{ClC6D5) ][B{C6F5) 4].
- 复合物1和2b,c显示光化学转化为桥接的-二元体.
- 复合体2d,具有硬质要求高的Cp*连接体,经历了轻易的热性正确C-H激活.
- 通过β-Cl清除和烯插入重新排列的Ortho-C-H激活产品.
结论:
- 在Cp*连接体中的绝缘阻碍促进了化复合体中的热正极-C-H激活.
- 光化学路径在较少阻碍的复合体中占主导地位.
- 这些发现提供了关于C-H激活机制和有机金属化学中的联结体效应的见解.
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