ja9b11597_si_004.cif (1.7 MB)
Download filePhenol Reduces Nitrite to NO at Copper(II): Role of a Proton-Responsive Outer Coordination Sphere in Phenol Oxidation
dataset
posted on 2020-01-14, 20:06 authored by Aditesh Mondal, Kiran P. Reddy, Jeffery A. Bertke, Subrata KunduIn
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.