双二氧化碳2和CS2的减少,由一个强大的双 () -1,8-纳菲西里丁连接体的二铜μ-复合体介导
Matthew S See1,2, Pablo Ríos1,3, T Don Tilley1,2
1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
Organometallics
|May 31, 2024
概括
一种新型的二核化配体 (PNNPFlu) 形成二铜复合体,在C-H键激活和CO2/CS2转换中表现出增强的反应性. 这些二铜μ-基物种由于协调球变化而增加活性,而不是Cu-B键变化.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 催化剂是一种催化剂.
背景情况:
- 开发用于稳定二铜物种的二核化配体.
- 在小分子激活 (CO2,CS2) 和C-H功能化中探索铜复合体.
- 在控制铜的反应性方面,现有的纳夫胺基联结物的局限性.
研究的目的:
- 合成和表征一种新型的二核化1,8-纳菲胺配体,具有与烯结合的氨酸侧臂 (PNNPFlu>).
- 研究产生的阴离子二铜复合物,特别是μ-衍生物,在C(sp) -H激活和CO2/CS2转化中的反应性.
- 阐明控制这些新型二铜种增强反应性的结构和电子因素.
主要方法:
- 合成PNNPFlu连接体及其相应的二铜复合体.
- 双铜μ-烯物种与迪博,西化异化物,CO2和CS2的反应2.
- 固态结构分析 (X射线晶体学) 和密度函数理论 (DFT) 计算.
主要成果:
- 成功合成了包含PNNP连接体的电离二铜复合体.
- 与相关系统相比,形成高度反应性的二铜μ-基物种 (4和5),表现出较高的C(sp) -H激活和CO2/CS2反应性.
- DFT分析和结构研究表明,增强的反应性源于协调球的修改,而不是Cu-B键的变化.
- 通过复合物4在diborane的存在下进行催化二氧化碳减排的证明.
- 从与CS2的反应中分离具有Cu-S-C-B连接的独特插入产品.
结论:
- PNNP流感配体有效地稳定了具有可调节的协调环境的反应性二铜物种.
- 来自PNNPFlu的二铜μ-烯复合体在C-H激活和小分子转化中显示了增强的催化活性.
- 协调球效应,特别是较低的协调数,对于这些铜系统中观察到的高反应性至关重要.
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