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Involvement of a Formally Copper(III) Nitrite Complex in Proton-Coupled Electron Transfer and Nitration of Phenols.

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A unique high-valent copper nitrite species, LCuNO2, was accessed via the reversible one-electron oxidation of [M][LCuNO2] (M = NBu4+ or PPN+). The complex LCuNO2 reacts with 2,4,6-tri-tert-butylphenol via a typical… Click to show full abstract

A unique high-valent copper nitrite species, LCuNO2, was accessed via the reversible one-electron oxidation of [M][LCuNO2] (M = NBu4+ or PPN+). The complex LCuNO2 reacts with 2,4,6-tri-tert-butylphenol via a typical proton-coupled electron transfer (PCET) to yield LCuTHF and the 2,4,6-tri-tert-butylphenoxyl radical. The reaction between LCuNO2 and 2,4-di-tert-butylphenol was more complicated. It yielded two products: the coupled bisphenol product expected from a H-atom abstraction and 2,4-di-tert-butyl-6-nitrophenol, the product of an unusual anaerobic nitration. Various mechanisms for the latter transformation were considered.

Keywords: electron transfer; proton coupled; electron; coupled electron

Journal Title: Inorganic chemistry
Year Published: 2022

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