芳香C-H键的分子间和分子内激活由二素和桥双核复合体
Ken-Ichi Fujita1, Hirohide Nakaguma, Taro Hamada
1Graduate School of Human and Environmental Studies, and Graduate School of Global Environmental Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
复合物经历C-H激活反应. 分子间激活发生在芳香溶剂中,而分子内激活观察到在dppm连接体中,从而产生新的有机金属结构.
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.
- 协调化学 协调化学
背景情况:
- 具有桥接连体的复合体是已知的催化剂.
- 在合成化学中,C-H激活是关键的转化.
- 了解连接体对反应性的影响至关重要.
研究的目的:
- 为了研究二核复合体与桥接dmpm和dppm连接体的反应性.
- 探索分子间和分子内C-H激活通路.
- 用结构方法来描述产生的产品.
主要方法:
- 复合体与基 (NaOtBu,Et2NH) 的反应.
- 使用芳香溶剂.使用芳香溶剂.
- 用X射线衍射进行结构确定.
主要成果:
- 观察到与[(Cp*Ir) 2 (((mu-dmpm) ((mu-H) 2) 2+和NaOtBu的分子间芳香C-H激活,形成新的Ir-Ar键.
- 在处理Et2NH时,在[(Cp*Ir) 2 ((mu-dppm) ((mu-H) 2) 2+的dppm连接体中的基组的分子内C-H激活.
- 通过X射线结晶学阐明关键产品3,5a和6的结构.
结论:
- 双核复合体表现出不同的C-H激活模式,这取决于桥接配体和反应条件.
- 该dmpm连接体促进分子间C-H激活与外部区域.
- 该dppm连接体可以经历分子内C-H激活,导致循环金属化物种.
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