期刊
INORGANIC CHEMISTRY
卷 61, 期 5, 页码 2662-2668出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03790
关键词
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资金
- National Institutes of Health [GM47365]
- NSF-MRI Award [CHE-1827756]
A unique high-valent copper nitrite species, LCuNO2, was obtained through oxidation reaction. LCuNO2 reacts with 2,4,6-tri-tert-butylphenol via a proton-coupled electron transfer reaction to yield LCuTHF and 2,4,6-tri-tert-butylphenoxyl radical. LCuNO2 reacts with 2,4-ditert-butylphenol to produce two products.
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.
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