Effect of Sterical Shielding on the Redox Properties of Imidazoline and Imidazolidine Nitroxides

• Published in: Journal of organic chemistry Vol. 80; no. 18; pp. 9118 - 9125
• Main Authors: Kirilyuk, Igor A, Bobko, Andrey A, Semenov, Sergey V, Komarov, Denis A, Irtegova, Irina G, Grigor’ev, Igor A, Bagryanskaya, Elena
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 18.09.2015
• Subjects: electrochemistry; hydroxylamine; organic chemistry; oxidants; regression analysis
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/acs.joc.5b01494

The oxidant properties of the series of 2,2,5,5-tetraalkyl imidazoline and imidazolidine nitroxides were investigated. An increase in the number of bulky alkyl substituents leads to a decrease in the rate of reduction with ascorbate, which makes the electrochemical reduction potential more negative and shifts the equilibrium in the mixture of nitroxide and reference hydroxylamine (3-carboxy-1-hydroxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl-1-15N) toward the starting compounds. The effect of structural factors on these reactions was analyzed by means of multiple regression using the Fujita steric constant E s and the inductive Hammett constant σI. Satisfactory statistical outputs were obtained in all of the biparameter correlations, denoting that the oxidant properties of the nitroxides are determined by steric and electronic effects of the substituents. The data imply that bulky substituents can stabilize nitroxide and/or destabilize hydroxylamine.