Further electrochemical investigations revealed an electrochemical-chemical (EC) mechanism, in which the stepwise reduction processes were found to be reversible but in the presence of Al(III) starting material (from the bulk solution) the electrochemically generated Al(I) species will chemically react in an irreversible manner. Exploration of the electrochemical properties of other low-oxidation state main group systems is ongoing, with a view to developing redox-based catalytic cycles at main group centres.