Abstract
The paramagnetic species formed by in situ electrochemical oxidation of eleven N-(o-nitrophenylthio) alicyclic amines in acetonitrile or propionitrile have been identified as the radical cations derived from the parent sulfenamides by one-electron transfer. The observed non-equivalence of the two N-methylene groups indicated the existence of restricted rotation around the S-N bond and three-electron π-bonded geometry. As regards the radical cations derived from six-membered alicyclic sulfenamides, the ring inversion was apparently conformationally frozen on the electron spin resonance (ESR) time scale even at 25°C. Based on the ESR and nuclear magnetic resonance data it is proposed that the C2N-S group in these radical cations is pyramidal and that the nitrogen inversion of these radicals is slow on the ESR time scale. The stability of the radical cations is discussed.
