HOMOGENEOUS REDOX CATALYSIS - APPLICATION TO THE KINETIC CHARACTERIZATION OF INTERMEDIATES UNDERGOING FAST BIMOLECULAR DECAY APPROACHING THE DIFFUSION LIMIT

The homogeneous redox catalysis method for determining the rate constants of fast reactions after the electron transfer step, which up to now has been used for monomolecular or pseudo-first order reactions, is extended to bimolecular reactions. Rate constants approaching the diffusion limit can be readily determined using the procedures proposed. The practical application of this method has been tested successfully using as an example the oxidation of N-benzyldihydronicotinamide, a synthetic analogue of NADH, and the deprotonation of its cation radical by benzylamine in acetonitrile.