Experimental and theoretical studies of the redox potentials of cyclic nitroxides

Blinco, James P., Hodgson, Jennifer L., Morrow, Benjamin J., Walker, James R., Will, Geoffrey D., Coote, Michelle L., & Bottle, Steven E. (2008) Experimental and theoretical studies of the redox potentials of cyclic nitroxides. The Journal of Organic Chemistry, 73(17), pp. 6763-6771.

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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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ID Code: 31134
Item Type: Journal Article
Refereed: Yes
Additional Information: This article is freely available from the American Chemical Society website 12 months after the publication date. See links to publisher website in this record.
Keywords: NMR Spectra, Non-nitroxide Intermediates, GAUSSIAN Archive Entries, B3-LYP/6-31G Optimised Geometrics
DOI: 10.1021/jo801099w
ISSN: 0022-3263
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Electrochemistry (030604)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > OTHER CHEMICAL SCIENCES (039900)
Divisions: Past > QUT Faculties & Divisions > Faculty of Science and Technology
Copyright Owner: Copyright 2008 American Chemical Society
Deposited On: 05 Mar 2010 00:54
Last Modified: 29 Feb 2012 13:51

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