Perpustakaan Digital ITB

Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high-energy radicalcations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron?proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radicalcation intermediates by supporting mechanisms that operate at electrode potentials much lower (?1 V) than those of analogous direct electrolysis reactions.