Mechanistic Variations in the Oxidation of Piloty's Acid by Metal Complexes

The reactions of N-hydroxybenzenesulfonamide (Piloty's acid, PA) with a variety of metal oxidants are reported. Either nitric oxide or nitrite is the final reaction product, along with benzenesulfinate and the reduced metal compound. The nitrogen product depends on the oxidation potential of the metal oxidant and its ability to further oxidize NO to nitrite. The observation and preliminary interpretation of unusual kinetic behavior of Piloty's acid as a reductant is also described. Analogues of PA were also prepared and found to show similar reactivity.