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

被引：13

作者：

Bouchey, Caitlin J. ^{[1
,2
]}

Tolman, William B. ^{[1
]}

机构：

[1] Washington Univ, Dept Chem, St Louis, MO 63130 USA

[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 05期

基金：

美国国家卫生研究院;

关键词：

CRYSTAL-STRUCTURE; TYPE-2; COPPER; SPECTROSCOPIC CHARACTERIZATION; DECOMPOSITION KINETICS; MOLECULAR-STRUCTURES; SUBSTRATE ADDUCT; SYNTHETIC MODEL; CU-II; REDUCTASE; REACTIVITY;

D O I：

10.1021/acs.inorgchem.1c03790

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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-ditert-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.

引用

页码：2662 / 2668

页数：7

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