Identification and characterization of intramolecular γ-halo interaction in d⁰ complexes: a theoretical approach

A mechanistic investigation to detect intramolecular M⋯X-C type interactions in d⁰ neutral and cationic complexes was carried out through a benchmark study employing different density functional methods. As γ-halogen is involved in M⋯X-C type interactions, it is denoted as a γ-halo interaction and the respective conformers are designated as halo-conformers. By analyzing the geometrical parameters of halo-conformers, it was observed that, irrespective of the nature of the metal and the halogen, the C_γ-X bond distance increases compared to the usual C-X bond, which brings the M and X centers close enough to generate a weak interaction. Generation of the M⋯X-C interaction was confirmed by performing NBO, AIM and Wiberg bond index analyses, from which the persistence of γ-halo interaction was seen to be prominent. Moreover, for each neutral and cationic complex, the values of Wiberg bond order are in good agreement with the AIM results. The effect of the metal center, as well as γ-halogen substitution, on γ-halo interaction was also studied in the present work. To justify the practical subsistence of the halo-conformers, we checked the stability of the conformers with respect to their β-conformers by comparing the zero-point-corrected electronic energies. Therefore, the entire study was designed in such a way that it can provide evidence in support of intramolecular M⋯X-C interactions, where, instead of the C-H bond, the C_γ-X bond will interact with the central transition metal.