基的多站点质子合电子转移激活中的速度驱动力关系
Guanqi Qiu1, Robert R Knowles1
1Department of Chemistry , Princeton University , Princeton , New Jersey 08544 , United States.
Journal of the American Chemical Society
|January 23, 2019
概括
这项研究详细介绍了基中的多位元质子合电子转移 (MS-PCET),揭示了协同激活机制. 这些发现挑战了马库斯理论,提出非完美的同步控制了反应速率.
科学领域:
- 摄影化学
- 有机化学
- 物理化学
背景情况:
- 激发状态的复合体是重要的电子捐赠者.
- 酸通过质子合电子转移 (PCET) 进行激活.
- 了解多站点PCET (MS-PCET) 的动力学对于合成应用至关重要.
研究的目的:
- 通过动力学研究基的MS-PCET激活.
- 开发一种结和PCET速率常数的提取方法.
- 探索PCET速率与反应驱动力的关系.
主要方法:
- 使用基于Ir (III) 的光催化剂的详细动力学研究.
- 发光灭实验以探测电子转移.
- 数据的解卷以确定平衡和速率常数.
主要成果:
- 基的MS-PCET激活通过协调的机制进行.
- 在PCET率和驱动力之间观察到线性相关性.
- 从马库斯理论的偏离表明非完美的同步效应.
结论:
- 证实了MS-PCET的协调性质.
- 不完美的同步为观察到的速度驱动力偏差提供了理由.
- 这些发现对使用MS-PCET设计高效的有机合成途径有影响.
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