The critical aspects
of the corrosion of metal electrodes in cathodic
reductions are covered. We discuss the involved mechanisms including
alloying with alkali metals, cathodic etching in aqueous and aprotic
media, and formation of metal hydrides and organometallics. Successful
approaches that have been implemented to suppress cathodic corrosion
are reviewed. We present several examples from electroorganic synthesis
where the clever use of alloys instead of soft neat heavy metals and
the application of protective cationic additives have allowed to successfully
exploit these materials as cathodes. Because of the high overpotential
for the hydrogen evolution reaction, such cathodes can contribute
toward more sustainable green synthetic processes. The reported strategies
expand the applications of organic electrosynthesis because a more
negative regime is accessible within protic media and common metal
poisons, e.g., sulfur-containing substrates, are compatible with these
cathodes. The strongly diminished hydrogen evolution side reaction
paves the way for more efficient reductive electroorganic conversions.