三坐标铜 (II) :在C-O键形成中的关键中间体
Subrata Kundu1, Christine Greene1, Kamille D Williams1
1Department of Chemistry, Georgetown University , Box 571227-1227, Washington, D.C. 20057, United States.
Journal of the American Chemical Society
|June 8, 2017
概括
合成和描述了新的铜 (II) 复合物. 这些中间体与氧化和酸盐离子反应,通过独特的铜介导途径使C-N键形成和乙烯合成.
科学领域:
- 有机金属化学
- 催化剂
- 合成化学
背景情况:
- 铜 (II) 类是铜催化交叉合反应中的关键中间体.
- 了解它们的结构和反应性是开发新合成方法的关键.
研究的目的:
- 合成和描述新的三坐标铜 (II) 复合物.
- 研究这些复合物与氧化和离子等小分子的反应性.
- 阐明C-N键形成和乙烯合成的机制.
主要方法:
- 铜氧化物和BC6F5的合成3.
- 结晶学,光谱学 (NMR,EPR) 和密度功能理论 (DFT) 的研究.
- 与气态氧化 (NO) 和酸 (PhO-) 的反应.
主要成果:
- 由β-二甲基胺酸支的新型三坐标铜(II) 烯的形成.
- 显示Cu (II) 有机金属复合物的独特几何和电子结构的特征.
- 通过NO成功形成C-N键,产生[Cu](eta(2) -ONC6F5).
- 从与酸盐的反应中直接合成二乙烯 (PhO-C6F5),包括氧化还原不成比例和Cu (I) 和短暂的Cu (III) 物种的形成.
结论:
- 合成的铜 (II) 烯复合物是有机金属转化中的多功能中间体.
- 这项研究提供了对铜介导的C-N合和乙烯形成的机理见解.
- 这项工作扩大了铜 (II) 有机金属化合物在催化中的反应范围.
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