Chemical and electrochemical reduction rates of cyclic nitroxides (nitroxyls)

The reduction rates of five-membered pyrrolidine and pyrroline, and six-membered piperidine nitroxides (alternatively termed nitroxyls) containing various substituents were determined under homogeneous conditions using ascorbate, and electrochemically under heterogeneous conditions. The results were compared with data from the literature. It was shown that the increased rates of reduction of six-membered nitroxides, compared with those of the five-membered nitroxides, cannot be explained on the basis of differences in electrochemical potentials but, rather, can be ascribed to differences in the accessibility of the nitroxide group. A double bond in the five-membered nitroxyls increases the reduction rate. Within any ring system, the reduction rates of nitroxides using ascorbate can be correlated with the inductive substituent constants. The half-way potentials for electrochemical reduction within a series of nitroxides based on the same ring correlate with logarithms of the rates using ascorbate and with the inductive constants. The potentials for one-electron oxidation of the nitroxides were related to the inductive constants.