Mixing 1 with 2 in C6D6 did not result in an observed reaction, neither at room temperature or at elevated temperature (50 °C). However, repetition of this attempted reaction in d8-THF (in line with electrochemical experiments) results in the formation of 3.THF, indicating oxidative addition of 2 at the Al(I) centre. Importantly here, we do not observe the disproportionation reaction of 3.THF back to 1 and 2. This contrasts with the report by Nikonov for the corresponding hydride system (Scheme 1B). On the basis of both NMR and electrochemical data, we postulate that the irreversible behaviour observed in the full electrochemical window (starting from 2, Figure ) is therefore the result of the chemical reaction between 1 and 2 to yield 3.THF (Scheme 2). Reversibility is only observed in the system in the absence of 2, as shown in Figure . To confirm this, we held the electrochemical cell at (B) -2.4 V vs. Ag for 10 minutes to generate 1 in larger quantities. This did not result in the formation of the distinctive dark red solution associated with 1, instead the solution remained yellow. Following synthetic work up and analysis of the 1 H NMR spectrum, 3.THF was confirmed to be the major product alongside trace amounts (< 5 %) of the THF ring opened product as reported by Nikonov. Thus, this confirmed the irreversible chemical reaction takes place between 1 and 2. This also provides a reasoning for the prolonged reaction times (72 hrs) and excess (>3 eq.) potassium metal that are required to access In conclusion, we have been able to establish an electrochemical set up that is compatible with low-oxidation state main group species. This allowed for the determination of the redox potentials and allowed for the isolation of the Al(II) intermediate via selection of an appropriate reducing agent.