After screening all possible univariate correlations, it was found that the angle () comprised by the Mn=O bond and the line connecting the Mn atom and H6 of the pyridine (coplanar with the Mn=O vector) moiety pointing towards the oxo (Figure ) correlates with the experimentally observed G ‡ values (R 2 = 0.79) (Figure ). The selected two-parameter model is composed by  and by the SterimolC5-R term that describes the general steric features of the pyridine unit along the C5-R axis at 5 Å. The  descriptor presents the highest coefficient (0.28) and has a positive correlation with enantioselectivity which suggests that an increase in  has a beneficial effect on enantioselectivity. The SterimolC5-R term also has a positive impact on enantioselectivity and carries a smaller coefficient (0.16). Consistent with other studies, this suggests that the positive effect on enantioselectivity associated to an increase in size of the substituent at position 5 of the pyridine moiety results from a restriction of the cone of trajectories available for the incoming substrate to reach the Mn=O unit. A second important consequence of the introduction of bulky substituents on the pyridines is a general improvement in the yield of P1, which can be reasonably attributed to an increased steric isolation of the metal center, which prevents or slows degradation pathways (Figure ). The subtle changes in  when modifying ligand architecture, translated into a significant impact on the observed enantioselectivity. For instance, the slight increase in  calculated by decreasing the electron-donating character of the pyridine as in [Mn V O(OAc)( NMe2,TIPS mcp)] 2+ (49.1º) and [Mn V O(OAc)( TIPS mcp)] 2+ (49.4º), or by changing the nature of the chiral diamine backbone as in [Mn V O(OAc)( TIPS ecp)] 2+ (49.9º), are in line with the observed increase in ee. As a result, the description of the system based on  values correlates well to the effect of electronic and structural modification of the catalyst with good predictivity (MAE of 0.09 kcal/mol).