Distinct differences in chemical oxidation and electrochemical oxidation reaction pathways may lead to isolation of different products. Chemical oxidants commonly participate in oxidative addition reactions which increase the co-ordination number whereas in non-coordinating solvents highly activated co-ordinatively unsaturated species can be generated by oxidation at an electrode surface. However, with electrochemical oxidation, the role of the so-called inert electrolyte anion such as perchlorate,tetrafluoroborate or hexafluorophosphate may be crucial. Novel aspects of electrochemical oxidation are illustrated by (i) the oxidation of amalgam electrodes in dichloromethane and benzene to generate highly activated cations which then form perchlorate, or tetrafluoroborate complexes prior to precipitation of neutral metal salts and (ii) oxidation of six co-ordinate zero valent chromium, molybdenum and tungsten complexes at platinum electrodes in the same solvents to produce co-ordinatively unsaturated oxidation state one and two species which are prone to nucleophilic attack by the perchlorate electrolyte. In contrast to differences observed in oxidation studies, chemical and electrochemical reduction pathways are likely to produce the same products because reductive elimination reactions can occur in both cases.