The configurational stability of biaryl motifs is addressed for the 1-naphthyl-N-benzimidazolyl motif substituted by a single diphenylphosphinyl group at the 2-position. The atropoenantiomers of the N-methylated cation H-MIOP, a less sterically locked analogue of the neutral H-MOP ligand, were resolved by enantiospecific cleavage of the N2CP bond of the resolved enantiomers of BIMIONAP. The latter were obtained by enantiospecific N-methylation of the previously resolved enantiomers of neutral BIMINAP. PdCl2 complexes of the P,C-chelating N-heterocyclic carbene (NHC)–phosphine ligands derived from (R)- and (S)-H-MIOP were prepared by two enantiospecific routes: by N2CP bond cleavage from the (R)- and (S)-BIMIONAP–PdCl2 complexes, or by simultaneous coordination of the P and C atoms of the in situ generated free NHC–phosphine. The enantiomerization pathways of H-MOP, H-MIOP, and corresponding NHC–phosphine have been investigated at the B3PW91/6-31G(d,p) level of theory. The calculated enantiomerization barriers of H-MOP and H-MIOP in acetonitrile are equal to 176.0 and 146.4 kJ mol−1, respectively, and are mainly determined by the distortion of the naphthalene and/or benzimidazole motifs in the transition state. Beyond the stability of their optical rotation at room temperature, the respective calculated Oki’s racemization temperatures of 334 and 225 °C allowed us to consider both ligands as configurationally stable.