Experimental and theoretical studies of the redox potentials of cyclic nitroxides

James P. Blinco, Jennifer L. Hodgson, Benjamin J. Morrow, James R. Walker, Geoffrey D. Will, Michelle L. Coote, Steven E. Bottle

    Research output: Contribution to journalArticlepeer-review

    134 Citations (Scopus)

    Abstract

    (Chemical Equation Presented) The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.

    Original languageEnglish
    Pages (from-to)6763-6771
    Number of pages9
    JournalJournal of Organic Chemistry
    Volume73
    Issue number17
    DOIs
    Publication statusPublished - 5 Sept 2008

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