DFT calculations were performed on the sandwich complexes of naphthalene (MNC) with alkali metal cation (Li⁺ /Na⁺ /K⁺) on one π face and the tripodal Cr(CO)₃ moiety on the other with a view to explore the role of cation on haptotropic migration. Cation binding not only enhances the complex interaction energy but also delicately affects the fluxionality in the molecule by increasing the barrier to haptotropic shift of Cr(CO)₃. The competing nature of the bifacial acids with sandwiched aromatic ring is established. In line with Pearson’s HSAB principle, LiNC system with highest interaction energy is found to be the most stable one among all the systems under study.
