Organic reactions utilizing electron transfer processes and the catalytic control

When electron transfer from a nucleophile (reductant) to an electrophile (oxidant) is energetically feasible, the electron transfer precedes a polar pathway to produce a radical ion pair, which leads to the final products via the follow-up steps involving cleavage and formation of chemical bonds. The follow -up steps are usually sufficiently rapid to render the initial electron transfer the rate-determining step in an overall irreversible transformation. The rate-determining electron transfer step can be accelerated by a catalyst which can interact with one of the electron transfer products. Both thermal and photochemical redox reactions which would otherwise be unlikely to occur are made possible to proceed efficiently by the catalysis on the electron transfer steps. The fundamental concepts of catalysis on electron transfer are presented and the mechanistic viability is described by showing a number of examples of both thermal and photochemical reactions that involve catalyzed electron transfer processes as the rate-determining steps.