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Phenol Reduces Nitrite to NO at Copper(II): Role of a Proton-Responsive Outer Coordination Sphere on Phenol Oxidation
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-01-08 , DOI: 10.1021/jacs.9b11597
Aditesh Mondal 1 , Kiran P Reddy 1 , Jeffery A Bertke 2 , Subrata Kundu 1
Affiliation  

In the view of physiological significance, the transition metal-mediated routes for nitrite (NO2-) to nitric oxide (NO) conversion and phenol oxidation are of prime importance. Probing the reactivity of substitued phenols towards nitrito copper(II) cryptate [mC]Cu(κ2-O2N)(ClO4) (1a), this report illustrates NO release from nitrite at copper(II) following a proton-coupled-electron-transfer (PCET) pathway. Moreover, a different protonated state of 1a with a proton hosted at an outer coordination sphere [mCH]Cu(κ2-O2N)(ClO4)2 (3) also reacts with substituted phenols via a primary electron-transfer from the phenol. Intriguingly, the alternative mechanism operative due to the presence of a proton at the remote site in 3 facilitates an unusual anaerobic pathway for phenol nitration.

中文翻译:

苯酚将铜 (II) 处的亚硝酸盐还原为 NO:质子响应外配位球对苯酚氧化的作用

从生理学意义来看,过渡金属介导的亚硝酸盐 (NO2-) 向一氧化氮 (NO) 转化和苯酚氧化的途径至关重要。探讨取代酚对亚硝基铜 (II) 穴状化合物 [mC]Cu(κ2-O2N)(ClO4) (1a) 的反应性,本报告说明了在质子耦合电子转移后铜 (II) 处亚硝酸盐的 NO 释放(PCET) 途径。此外,质子位于外配位球 [mCH]Cu(κ2-O2N)(ClO4)2 (3) 的 1a 的不同质子化状态也通过苯酚的初级电子转移与取代苯酚反应。有趣的是,由于在 3 中远程站点存在质子而起作用的替代机制促进了苯酚硝化的不寻常厌氧途径。
更新日期:2020-01-08
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