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Electrons and Holes as Catalysts in Organic Electrosynthesis
Author(s) -
Francke Robert,
Little R. Daniel
Publication year - 2019
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201900432
Subject(s) - electrosynthesis , redox , reagent , ionic bonding , electron , catalysis , chemistry , chemical physics , electron exchange , radical ion , cathode , stoichiometry , combinatorial chemistry , ion , electrode , substrate (aquarium) , atom (system on chip) , photochemistry , inorganic chemistry , organic chemistry , electrochemistry , physics , computer science , quantum mechanics , oceanography , embedded system , geology
Abstract The injection (or removal) of electrons into (or from) a substrate by an electrode can effectively catalyze various redox‐neutral reactions that otherwise require harsh conditions and/or the use of reagents. Such processes involve the electrogeneration of an ionic or radical ionic species, which after a coupled chemical step either undergoes a backward electron exchange with the electrode (ECE b mechanism) or triggers a chain process in the bulk solution. Under these circumstances, sub‐stoichiometric amounts of charge are sufficient to achieve a full conversion and conceptionally, the electrons and holes can be understood as being catalysts. This principle has been successfully applied to accomplish a number of redox‐neutral transformations such as molecular rearrangements, Diels‐Alder‐type cycloadditions and radical substitution reactions (S RN 1) in a mild and atom‐economical fashion. Although examples have been reported but sporadically since the early 1970s, a number of exciting recent developments have led us to review and discuss these cases using unifying mechanistic concepts that are described herein.