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The oxidation and reduction potentials of a variety of carbon-centered radicals have been measured by a technique that makes use of modulated photolysis for radical generation and phase-sensitive voltammetry for their detection. The measured half-wave potentials were close to the thermodynamically significant E°values for the arylmethyl radicals and led to estimates of pATa(RH) and pATR(ROH) as well as data for the solvation energies of these ions and radicals.The electron donor and acceptor properties of a molecule in the gas phase are characterized by the ionization potential, IP,2 and electron affinity, EA.3 However, these properties are not directly relevant to the liquid phase where solvation of ions becomes important. In fact, the solution analogues of the ionization potential and electron affinity of a molecule are the electrochemical oxidation and reduction potentials4 which, for the vast majority of persistent molecules, are easily measured by standard techniques.

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Die gegenüber den entsprechenden Kohlenwasserstoffen und strukturgleichen Ethem reaktionsfreudigeren Amine wie z.B. Triethylamin, Triethylendiamin, Pyrrolidin und tert‐Butylamin liefern Geschwindigkeitskonstanten zwischen 3.3 ‐ 10°C ‐4.4‐ 109 /M‐s für die Titelreaktionen.

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