Simultaneously, the H-bonding interactions between the carbonyl group of the amide substituent with distances of 2.25 and 1.99 Å (TS major ), and 2.25 and 2.01 Å (TS minor ) become weaker as a result of the increased electron density determined by the tetradentate ligand that presumably renders the α-N C-H bonds engaging in H-bonding less acidic. As expected, the calculated  in the TS major of [Mn V O(OAc)( NMe2 pdp)] 2+ (47.8º) is lower than that calculated for the [Mn V O(OAc)(pdp)] 2+ (48.4º) system, which matches what the MLR model would predict for this less enantioselective catalyst.