ETC: A Mechanistic Concept for Inorganic and Organic Chemistry

Abstract

AbstractThe concept of electron transfer catalysis (ETC), or more specifically “Double Activation Induced by Single Electron Transfer” (DAISET) gives an opportunity to connect experimental facts never previously correlated. The first activation results from the transfer of an electron to (or from) a molecular species; the second activation results from the build‐up of a reaction chain able to reproduce the species formed in the first step. The starting point of this review is the SRN1 mechanism where principle and experimental diagnostic criteria are critically discussed. The thermal and photochemical exchange and substitution reactions of PtIV complexes are then reviewed together with the exchange reaction [AuCl4]−/Cl−, reactions with Grignard reagents and other organometallic reagents, as well as the redox behavior of electronically excited organic compounds. Photochemical applications, including solar energy conversion are discussed. New aspects are also presented for the mechanistic problem “SN2 reaction or SET process?” Moreover, the concept has significance for SH2 reactions at metal centers, molecule‐induced homolyses, reactions of complexes, as well as electrochemical processes.–Unless otherwise specified, only double activation (DAISET) processes will be discussed in this article.