Fc/Fc + . This is in line with expected values, considering the highly reducing conditions required to access Al(I) experimentally. As the CV data shows, this Al(III) to Al(I) reduction process occurs in a stepwise manner via a likely Al(II) intermediate. Thus, we have investigated the proposed Al(II) intermediate using a combined synthetic and electrochemical approach. First, using the redox potentials gained from the CV data we opted for a slightly milder reducing agent in sodium [reduction potentials -2.71 V (Na); -2.92 V (K) vs. standard hydrogen electrode (SHE)], as this should allow for the reduction of Al(III) to the putative Al(II) species but Na is not reducing enough to access Al(I) in this ligand framework. Reduction of 2 using 1.2 eq. 5% Na/NaCl in toluene led to the isolation of a new, pale-yellow complex (3) after 72 hrs at room temperature. Compound 3 was characterised by multinuclear and 2D NMR spectroscopy as well as UV-vis spectroscopy, unfortunately attempts at growing crystals suitable for single crystal Xray crystallography failed. Its 1 H NMR spectrum looks very similar to that of the starting material, with only a marginal shift in the β-diketiminate methine from δ 5.06 ppm (1) to δ 5.07 ppm (3). However, H DOSY NMR reveals a clear difference in molecular weights with compound 3 almost double the (A) (B) estimated mass of 1. Thus, we propose that 3 is the dimeric [LAlI]2 Al(II) species, akin to the previously reported [LAlH]2 (3-H) dimer. As further proof that this species (3) is Al(II), we took the isolated compound 3 and reduced it with KC8. On monitoring the 1 H NMR spectra 30% conversion to 1 was observed after 2 hrs, reaching a maximum of 39% conversion after 19 hrs then showed no further increase. In order to match the electrochemical set up, which is performed in THF, we were also able to synthetically reduce 2 in THF using 1 eq. of KC8. This led to the monomeric species with one THF coordinated (3.THF), as confirmed by NMR spectroscopy. Importantly, 3.THF can be isolated from the electrochemical cell when the cell is held at -1.8 V for 15 minutes, to allow for build-up of 3.THF in solution prior to its isolation.