Abstract
A unique high-valent copper nitrite species, LCuNO(2), was accessed via the reversible one-electron oxidation of [M][LCuNO(2)] (M = NBu(4)(+) or PPN(+)). The complex LCuNO(2) 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 LCuNO(2) 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.