含有四胺宏环联体的 (VI) 复合物的结构和反应性
Huatian Shi1, Hung Kay Lee2, Yi Pan1
1Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
Journal of the American Chemical Society
|September 9, 2021
概括
这项研究报告了一种罕见的 (VI) 化物复合物,MnVI 这种稳定的复合物表现出独特的反应性,在N原子转移和化物转移反应中充当电友和核友.
科学领域:
- 无机化学
- 有机金属化学
- 化学
背景情况:
- +6氧化状态的复合物非常罕见,通常不稳定.
- 之前的化复合物在溶液中产生,但太不稳定,无法分离.
研究的目的:
- 隔离和描述一个稳定的 (VI) 化物复合物.
- 在N原子和化物转移反应中研究分离的Mn (VI) 化物复合物的活性.
- 用NADH类似物阐明化物转移反应的机制.
主要方法:
- 一个MnV) 基前体的单电子氧化生成MnVI) 复合体.
- 用X射线结晶学进行结构测定.
- 与素,烯和NADH类似物发生反应.
- 哈梅特研究和动态同位素效应测量.
- 电喷离子质谱 (ESI/MS) 和红外 (IR) 光谱.
主要成果:
- 一个稳定的Mn (VI) 化物复合物的X射线结构特征,Mn (VI) 化物复合物.
- 已证明N原子转移到三和烯,形成Ph3PNH和亚齐里丁
- 在与替代烯 (V形哈梅特图) 的反应中观察到的电友和核友行为.
- 与NADH类似物 (AcrH2和BNAH) 进行成功的化物转移反应,其动态同位素效应为7.3.
- 产品的特征 [MnV(N)
结论:
- 这项研究成功地分离并表征出一种罕见且稳定的化复合物.
- 该复合物具有多功能反应性,包括N原子转移和化物转移.
- 化物转移反应通过"分离协同质子电子转移" (CPET) 机制进行,质子转移到TAML联体的碳氧.
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