与碳-碳键形成反应相关的分离有机金属 (III) 和 (IV) 复合物
Jason W Schultz1, Kei Fuchigami1, Bo Zheng1
1Department of Chemistry, Washington University , One Brookings Drive, St. Louis, Missouri 63130-4899, United States.
Journal of the American Chemical Society
|September 7, 2016
概括
这项研究报告了第一个孤立的 (III) -二甲基复合物,证明其在碳-碳键形成中的作用. 这些发现表明 (III) 和 (IV) 种在催化交叉合反应中具有关键作用,特别是与基质.
科学领域:
- 有机金属化学
- 催化剂
- 合成有机化学
背景情况:
- 由于其与电友和立体化学控制的多功能性,催化在交叉合反应中越来越突出.
- 与不同,催化剂很容易进入多个氧化状态,包括奇数电子配置,通常提出Ni (III) 中间体.
研究的目的:
- 隔离和表征一个Ni (III) -dialkyl复合物.
- 研究催化交叉合反应中和可能更高的氧化状态在C-C键形成中的作用.
主要方法:
- 一个Ni (III) -dialkyl复合物的分离和表征.
- 固体测量和催化C-C键形成的研究.
- 短暂的Ni (IV) 物种的光谱观测和特征.
主要成果:
- 第一个Ni (III) - 双基复合物被成功分离出来.
- 这种Ni (III) 复合物在固体测量和催化C-C键形成方面都表现出活性.
- 氧化剂的添加加快了C-C键的形成,涉及过渡的Ni (IV) 物种.
- 在一个循环系统中通过光谱观察到一个Ni (IV) 物种.
结论:
- 孤立的Ni (III) - 双基复合物是C-C键形成中的可行的中间体.
- 过渡性Ni (IV) 种可能在催化交叉合中发挥重要作用,特别是与基底.
- 对于理解催化交叉合机制,Ni (III) 和Ni (IV) 的氧化状态都很重要.
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