Importance of Dispersion on the Stability of the Concave-Bound CpM (M = Fe, Ru, Os) Complexes of Sumanene

The preference for concave mode binding of the CpM unit with sumanene in CpM(eta(6)-sumanene)(+) (M = Fe, Ru, Os) over the convex mode is analyzed by various density functional theory based methods including (or not) dispersion and solvent effects. In the case of the iron complex, the concave-bound isomer becomes energetically more favorable than the convex form only after the proper inclusion of dispersion effects, highlighting the importance of such contributions to stabilize the former arrangement. For the ruthenium complex, both the dispersion and solvent effects should be taken into account to provide a correct trend. The noncovalent interaction index corroborates the role of dispersion in concave selectivity. Our computations also show that the presence of the counterion is not relevant for this selectivity, discarding the previously reported argument made by Okumura et al.