Density Functional Theory (DFT) studies were undertaken using Gaussian 16 with BP86 optimised structures, alongside electronic structure analyses completed with NBO7 (see ESI for full computational details). Relative free energies of the [AE{N(SiMe3)2}3] -monoanion and the proposed reduced [AE{N(SiMe3)2}3] 2-dianion (Scheme 3) were calculated and confirm the reduction to be exergonic in nature (Ca: -20.5 kcal/mol; Sr: -20.2 kcal/mol; Ba: -22.1 kcal/molsee Table in ESI). Molecular Orbital analysis of the [AE{N(SiMe3)2}3] - ). These structural differences could be due to mesityl substituent conformations in each amide ligand as observed in precursors 3-AE (vide supra), with this puckering affecting an increase or decrease in the dcharacter of calculated SOMOs based on steric effects. A similar puckering was also observed in the solid state structure of [Y{N(SiMe3)2}3] -([Kr]4d 1 ) reported by Evans and co-workers, which could be considered as isoelectronic to [Sr{N(SiMe3)2}3] 2-. Conversely, [Sc{N(SiMe3)2}3] -([Ar]4d 1 ), isoelectronic to [Ca{N(SiMe3)2}3] 2-, displays a regular trigonal planar geometry. For completeness, the same computational studies were performed on Mg analogues, which also afforded an exergonic reaction profile for the reduction to Mg(I) (-14.5 kcal/mol), though to a lesser extent compared to the heavier analogues, and reassuringly no d-orbital contributions observed in the MOs. Interestingly, in the case of [AE{N(Mes)(SiMe3)}3] - monoanions the ΔG of the reduction is affected by the orientation of the mesityl substituents.