Experimental and theoretical studies of the redox potentials of cyclic nitroxides
Data(s) |
2008
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Resumo |
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. |
Identificador | |
Publicador |
American Chemical Society |
Relação |
DOI:10.1021/jo801099w 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. |
Direitos |
Copyright 2008 American Chemical Society |
Fonte |
Faculty of Science and Technology |
Palavras-Chave | #030604 Electrochemistry #039900 OTHER CHEMICAL SCIENCES #NMR Spectra #Non-nitroxide Intermediates #GAUSSIAN Archive Entries #B3-LYP/6-31G Optimised Geometrics |
Tipo |
Journal Article |