The effect of cation concentration on the nitrogen splitting constant of nitroxide free radicals

Abstract

Nitroxide free radicals prepared from diethylamine, piperidine and pyrrolidine by oxidation with hydrogen peroxide were studied by ESR spectroscopy. The changes in the 14N splitting constant (aN) caused by the addition of KBr or tetraethylammonium bromide were measured in dependence on the concentration of the ions. For diethylamine nitroxide and piperidine nitroxide, the results are discussed in terms of two equilibria: the one, involving the anion, is associated with a gain or loss of hydrogen bonds to the nitroxide oxygen atom, the other is associated with the formation of solvent shared units involving the cation, which results in changes in the hydrogen bonding strenght. The large increase in the aN value in the case of pyrrolidine nitroxide is explained in terms of an interaction from one side of the positively charged N atom; the increase in aN in the case of diethylamine and piperidine nitroxides is explained in terms of interactions with both sides of the positively charged N atom.