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Phenol Reduces Nitrite to NO at Copper(II): Role of a Proton-Responsive Outer Coordination Sphere in Phenol Oxidation

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posted on 14.01.2020, 20:06 authored by Aditesh Mondal, Kiran P. Reddy, Jeffery A. Bertke, Subrata Kundu
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 substituted phenols toward the nitritocopper­(II) cryptate complex [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 in the outer coordination sphere, [mCH]­Cu­(κ2-O2N)­(ClO4)2 (3), also reacts with substituted phenols via primary electron transfer from the phenol. Intriguingly, the alternative mechanism operative because of the presence of a proton at the remote site in 3 facilitates an unusual anaerobic pathway for phenol nitration.