电子和介质对亚伦C[键]H激活率的电子和介质影响,由阴离子Ir (III) 复合体激活
David M Tellers1, Cathleen M Yung, Bruce A Arndtsen
1Division of Chemical Sciences, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA.
Journal of the American Chemical Society
|February 14, 2002
概括
这项研究揭示,复合物通过离子对机制激活中C-H键,其中三解离会先于激活. 通过在复合体和基基底上提供电子的替代物来增强反应性.
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.
- 反应机制 反应机制
背景情况:
- 烯C-H激活是有机金属化学中的一个关键转换.
- 了解机械路径是设计高效催化剂的关键.
研究的目的:
- 研究二甲溶液中的Cp(L) IrMe(X) 复合体对烯C-H激活的详细机制.
- 阐明离子对形成和连接物解离在催化循环中的作用.
主要方法:
- 使用Cp(L) IrMe(X) 复合物的详细机理研究,具有不同的配体 (L) 和对子体 (X).
- 在CH(2)Cl(2) 溶液中的动力分析,包括添加盐的研究,以探测离子对相互作用.
- 密度函数理论 (DFT) 计算以支持机械解释.
主要成果:
- 在C-H激活之前,三酸盐与Cp (L) IrMe (OTf) 分离,形成离子对.
- 反应性取决于介质,可以通过使用弱协调的阳离子 (如BAr{f}) 的"特殊盐效应"显著增强.
- 电子捐赠替代物增加了C-H激活率,而氨酸配体的电子效应主要影响了平衡前配体解离.
结论:
- C-H激活机制涉及初始的三叶酸解离,以形成化中间体.
- 整体反应速率通过在复合体和基基底上提供电子的组来优化.
- DFT计算支持所提出的机械模型,强调了连接体可变性和离子配对的重要性.
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