Redox and Acidity Properties of Alkyl- and Arylamine Radical Cations and the Corresponding Aminyl Radicals
Autor: | Janusz Lusztyk, Mats Jonsson, and D. D. M. Wayner |
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Rok vydání: | 1996 |
Předmět: | |
Zdroj: | The Journal of Physical Chemistry. 100:17539-17543 |
ISSN: | 1541-5740 0022-3654 |
DOI: | 10.1021/jp961286q |
Popis: | In this work the pKas of six alkyl- and arylamine radical cations in aqueous solution have been determined by means of laser flash photolysis. The corresponding N-nitrosamines were used as precursors for the aminyl radicals which, upon protonation, formed the amine radical cations. The following pKas were obtained: 3.6 ± 0.2, 7.6 ± 0.3, 6.8 ± 0.5, 5.3 ± 0.5, 5.5 ± 0.5, and 5.8 ± 0.5 for the radical cations of diphenylamine, N-methylaniline, dimethylamine, diethylamine, pyrrolidine, and piperidine, respectively. In addition, the peak oxidation potentials of diphenylamine, N-methylaniline, aniline, diethylamine, pyrrolidine, and piperidine have been measured in aqueous solution and in acetonitrile using cyclic voltammetry. Furthermore, the one-electron reduction potentials of the diphenylaminyl radical and the N-methylanilinyl radical in acetonitrile were measured using photomodulation voltammetry. The results of this study and of previously published studies are discussed in terms of relative substituent and solvent effects. |
Databáze: | OpenAIRE |
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