Predicting Electrocatalytic Properties: Modeling Structure–Activity Relationships of Nitroxyl Radicals

Stable nitroxyl radical-containing compounds, such as 2,2,6,6-tetramethylpiperidine-<i>N</i>-oxyl (TEMPO) and its derivatives, are capable of electrocatalytically oxidizing a wide range of alcohols under mild and environmentally friendly conditions. Herein, we examine the structure–function relationships that determine the catalytic activity of a diverse range of water-soluble nitroxyl radical compounds. A strong correlation is described between the difference in the electrochemical oxidation potentials of a compound and its electrocatalytic activity. Additionally, we construct a simple computational model that is able to accurately predict the electrochemical potential and catalytic activity of a wide range of nitroxyl radical derivatives.