高反应性基复合物:C-H和H-H键的激活
Weiqing Mao1, Li Xiang1, Carlos Alvarez Lamsfus2
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
Journal of the American Chemical Society
|January 10, 2017
概括
合成了第一个scandium phosphinoalkylidene复合物,具有最短的sc-c键并使c-h激活反应成为可能. 这一发现为有机金属化学和催化开辟了新的途径.
科学领域:
- 有机金属化学
- 无机化学
背景情况:
- 复合物越来越多地被研究为独特的反应性.
- 基联体提供了新的协调模式.
研究的目的:
- 合成和表征第一个基复合物.
- 为了研究它的C-H键激活能力.
主要方法:
- 合成和单晶X射线衍射的复合物.
- 密度函数理论 (DFT) 的计算.
- 反应性研究包括C-H激活和H2激活.
主要成果:
- 首个基复合物已成功合成和表征.
- 该复合体显示了迄今为止报告的最短的-碳键长度.
- 在室温下观察到皮里丁,4- dimethylamino pyridine和1,3- dimethylpyrazole的分子间C- H键激活.
- 在温和的条件下实现了H2的快速激活.
- DFT计算揭示了三中心π相互作用和对1,3-二甲基醇的CH激活的选择性.
结论:
- 这种新型的基复合体在C-H激活和H2激活方面具有显著的潜力.
- 电子结构和硬质因素影响这些转换的反应性和选择性.
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