Department of Chemistry , University of Wisconsin - Madison , 1101 University Avenue , Madison , Wisconsin 53706-1322 , United States.
J Org Chem. 2018 Jul 20;83(14):7323-7330. doi: 10.1021/acs.joc.7b02547. Epub 2017 Dec 13.
Electrochemical studies of the reduction and oxidation reactions of five different organic nitroxyls have been performed across a wide pH range (0-13). The resulting Pourbaix diagrams illustrate structural effects on their various redox potentials and on the p K values of the corresponding hydroxylamine and hydroxylammonium ions. Evidence is also given for the reversible formation of a hydroxylamine N-oxide when nitroxyls are oxidized in alkaline media. Structural effects on the thermodynamics of this reaction are assessed.
电化学研究了还原和氧化反应的五个不同的有机氮氧自由基在很宽的 pH 值范围内（0-13）。由此产生的 Pourbaix 图说明了它们的各种氧化还原电位和相应的羟胺和羟铵离子的 pK 值的结构效应。也有证据表明，当氮氧自由基在碱性介质中被氧化时，可逆地形成羟胺 N-氧化物。评估了这种反应热力学的结构效应。
