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1 January 2006 Kinetic Determinations of Accurate Relative Oxidation Potentials of Amines with Reactive Radical Cations
Ian R. Gould, Zofia M. Wosinska, Samir Farid
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Abstract

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, Ep, rather than thermodynamically meaningful oxidation potentials, Eox. In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated Eox by correcting the Ep from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

Ian R. Gould, Zofia M. Wosinska, and Samir Farid "Kinetic Determinations of Accurate Relative Oxidation Potentials of Amines with Reactive Radical Cations," Photochemistry and Photobiology 82(1), 104-109, (1 January 2006). https://doi.org/10.1562/2005-06-14-RA-571
Received: 14 June 2005; Accepted: 17 July 2005; Published: 1 January 2006
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