Experimental and theoretical studies of the redox potentials of cyclic nitroxides |
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Authors: | Blinco James P Hodgson Jennifer L Morrow Benjamin J Walker James R Will Geoffrey D Coote Michelle L Bottle Steven E |
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Institution: | Australian Research Council Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland, 4001, Australia. |
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Abstract: | 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. |
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