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

Stable
nitroxyl radical-containing compounds, such as 2,2,6,6-tetramethylpiperidine-N-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.