热惰性循环金属化Ru的光化学分辨率
Lucien N Lameijer1, Corjan van de Griend1, Samantha L Hopkins1
1Leiden Institute of Chemistry, Leiden University , Einsteinweg 55 , 2333CC Leiden , The Netherlands.
Journal of the American Chemical Society
|December 12, 2018
概括
这项研究引入了一种用于分离性有机金属 (II) 复合物的新光替代方法. 这种光化学策略使得二态异构体的分离成为可能,为性复合合成提供了一种新的合成途径.
科学领域:
- 有机金属化学
- 摄影化学
- 基质合成
背景情况:
- 体有机金属复合物在催化和材料科学中至关重要.
- 解决奇拉复合体的传统方法,如热联体交换,由于键的惰性,通常是无效的.
- ((II) 循环金属化复合物具有独特的结构和光化学特性.
研究的目的:
- 开发一种光替代策略来分离的有机金属复合物.
- 合成和表征一系列的环金属化 (II) 复合物.
- 研究这些复合物的光化学行为,并了解影响光替代的因素.
主要方法:
- 合成和表征五个循环金属化 ((II) 复合物:Ru ((phbpy)) ((N-N)) ((DMSO-κS)) ((PF6).
- 由可见光辐射诱导的光替代反应.
- 使用奇拉硫化物的热协调,然后通过逆相HPLC分离异构体进行奇拉分辨.
主要成果:
- 在5个合成的复合物中,有3个 ([1]PF6-[3]PF6) 经过选择性光置换.
- 在特定的复合物中,通过光化学方法成功地实现了二立体同位素的奇拉分辨率.
- 光化学,电化学和边界轨道分析解释了复合体之间的不同光化学惰性.
结论:
- 光替代提供了一种可行的替代热方法来解决性有机金属复合物.
- 这种光化学方法为合成纯循环金属化 (II) 复合物提供了新的途径.
- 了解控制光置换的电子和结构因素是设计新合体的关键.
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