由 (Ph3P) 6Cu6H6的氧化产生的离子铜
Shuo Liu1, Michael S Eberhart1, Jack R Norton1
1Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.
Journal of the American Chemical Society
|May 31, 2017
概括
从六核铜集群到氧化剂的电子转移对于第一个电子来说是快速的,但对于第二个电子来说是显著的慢. 这项研究详细介绍了由此产生的氧化铜集群结构及其合成.
科学领域:
- 有机金属化学
- 协调化学
- 电子转移反应
背景情况:
- 六核铜集群,如 (Ph3P) 6Cu 6H6,由于其独特的结构和反应性而引起了人们的兴趣.
- 了解这些集群中的电子转移过程对于它们在催化和材料科学中的应用至关重要.
研究的目的:
- 研究从 (Ph3P) 6Cu6H6到Cp*2Fe+的连续电子转移的动力学和热力学.
- 描述产生的氧化铜化物种的结构.
- 探索这些氧化集群的替代合成途径.
主要方法:
- 使用Cp*2Fe+作为一个电子氧化剂的电化学氧化研究.
- 电子转移速率的动力分析.
- 通过X射线衍射进行结构特征.
- 化学合成和表征 (微分析,转化反应).
主要成果:
- 从 (Ph3P) 6Cu6H6的第一个电子转移非常快 (k > 10^6 L·mol^-1·s^-1).
- 由于较低的热力学驱动力,第二个电子转移显著较慢 (k = 9.29(4) × 10^3 L·mol^-1·s^-1),形成[(Ph3P) 6Cu6H5]+.
- 在不同氧化条件下形成的[{Ph3P) 6Cu6H5]+的二面体结构和[{Ph3P) 7Cu7H6]+的封顶八面体结构得到了X射线衍射证实.
结论:
- 从 (Ph3P) 6 Cu 6 H6 的顺序电子转移呈现出不同的动力和热力学配置.
- 这项研究为氧化铜化集群提供了详细的结构见解.
- 建立了这些集群的替代合成途径,提高了它们的可访问性.
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