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

doi:10.1021/jo801099w

Back

Experimental and theoretical studies of the redox potentials of cyclic nitroxides

Journal article

Peer reviewed

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 and Steven E Bottle

The Journal of Organic Chemistry, Vol.73(17), pp.6763-6771

2008

DOI: https://doi.org/10.1021/jo801099w

PMID: 18683980

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.

Details

Title: Experimental and theoretical studies of the redox potentials of cyclic nitroxides
Authors: James P Blinco (Author) - Queensland University of Technology
Jennifer L Hodgson (Author) - Queensland University of Technology
Benjamin J Morrow (Author) - Queensland University of Technology
James R Walker (Author) - Queensland University of Technology
Geoffrey D Will (Author) - Queensland University of Technology
Michelle L Coote (Author) - Queensland University of Technology
Steven E Bottle (Corresponding Author) - Queensland University of Technology
Publication details: The Journal of Organic Chemistry, Vol.73(17), pp.6763-6771
Publisher: American Chemical Society
DOI: 10.1021/jo801099w
ISSN: 1520-6904
PMID: 18683980
Grant note: Australian Research Council: CE0561607
Organisation Unit: School of Science, Technology and Engineering
Language: English
Record Identifier: 99737995802621
Output Type: Journal article