可以将化物降低到铜中的NO (II):氧化过程中对质子反应的外部协调球的作用
Aditesh Mondal1, Kiran P Reddy1, Jeffery A Bertke2
1School of Chemistry , Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM) , Thiruvananthapuram 695551 , India.
Journal of the American Chemical Society
|January 9, 2020
概括
这项研究揭示了铜复合物如何促进化物转化为氧化和氧化. 观察到一个与质子合的电子转移通路,使得独特的无氧化.
科学领域:
- 生物有机化学
- 有机金属化学
- 催化剂
背景情况:
- 过渡金属介导的反应对生理过程至关重要,包括化成氧化和氧化.
- 铜复合体在催化这些重要的化学转化中起着重要作用.
- 了解这些反应的机制是开发新催化系统的关键.
研究的目的:
- 调查替代与铜密复合物的反应性.
- 阐明由铜介导的酸盐释放的机制.
- 探索质子化状态对反应路径和产品的影响.
主要方法:
- 铜 (II) 密度复合物的合成和表征.
- 探测反应中间体和机制的光谱研究.
- 动力学研究以确定反应速度和顺序.
- 支持拟议的机制的计算分析.
主要成果:
- 从铜 ([mC]Cu) 复合物 ([mC]Cu) 释放的化物到氧化 (NO) 通过与替代相结合的电子转移 (PCET) 途径进行.
- 一个质子化铜 ([mCH]Cu) 复合体通过从的初始电子转移与反应.
- 在铜复合体的外部协调球体中存在一个质子,为酸的异常无氧路径提供便利.
结论:
- 化成氧化和氧化的机制高度依赖于铜催化剂的质子化状态.
- PCET是从铜化物中释放NO的关键途径.
- 复合铜可以调解新型无氧化反应.
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