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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Phenol Reduces Nitrite to NO at Copper(II): Role of a Proton-Responsive Outer Coordination Sphere in Phenol Oxidation
Aditesh Mondal1, Kiran P Reddy1, Jeffery A Bertke2
1School of Chemistry , Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM) , Thiruvananthapuram 695551 , India.
Abstract:
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.
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