Electrochemical Mechanisms of Dissociative Electron Transfer

Dissociative electron transfer constitutes a class of redox processes in which a substrate accepts one or more electrons at an electrode interface, triggering the cleavage of a covalent bond. Two principal pathways are distinguished: a concerted mechanism, wherein bond rupture and electron uptake occur in a single elementary step, and a stepwise sequence involving formation of a discrete radical-anion intermediate followed by bond lysis. The reaction course is influenced by molecular structure, solvation and proton-donor strength, and may proceed via coupled chemical steps (ECE mechanisms) or through distinct electron-transfer and chemical substeps. Electroanalytical methods, notably cyclic voltammetry and bulk electrolysis, combined with digital simulation and computational thermochemistry, have elucidated rate constants, standard potentials and bond dissociation energies. A deep mechanistic understanding informs applications ranging from selective organic transformations and small-molecule activation to energy-conversion devices and environmental remediation. By modulating electrode potential, proton availability and molecular design, researchers can steer reaction selectivity, optimise yields and uncover fundamental principles of bond activation under mild conditions.

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Electrochemical Mechanisms of Dissociative Electron Transfer publication trend

The graph below shows the total number of articles in electrochemical mechanisms of dissociative electron transfer across all publications each year (not limited to Nature Index journals).

Technical terms

Dissociative electron transfer: An electron-transfer event coupled to bond cleavage in a single or multistep sequence.

Radical anion: A negatively charged species hosting an unpaired electron, often pivotal in stepwise bond-breaking pathways.

Concerted mechanism: A pathway in which electron transfer and bond rupture occur simultaneously in one elementary step.

Stepwise mechanism: A sequence in which an initial electron-transfer generates a radical intermediate, followed by a separate bond-cleavage or protonation event.

Cyclic voltammetry: An electroanalytical technique that scans electrode potential to characterise redox behaviour and mechanistic features of electroactive species.

ECE mechanism: An electrochemical–chemical–electrochemical sequence where a chemical transformation intervenes between two electron-transfer steps.

References

1. Anion Radical of Carbonyl Compounds as Electrochemically Generated Base in Henry Reactions: 1,2-Acenaphthenedione. Journal of The Electrochemical Society (2020).
2. Dissociative Electron Transfer to Diphenyl-Substituted Bicyclic Endoperoxides: The Effect of Molecular Structure on the Reactivity of Distonic Radical Anions and Determination of Thermochemical Parameters. Molecules (2014).
3. Hydrogen Bonding and Proton Transfer Processes during the Electrochemical Reduction of Nitrosobenzene in Acetonitrile. ChemElectroChem (2025).