Bond Dissociation Energies Reveal the Participation of d Electrons in f-Element Halide Bonding

Bond dissociation energies (BDEs) reported in the literature for lanthanide monofluorides and lanthanide monochlorides LnX, where X = F or Cl, exhibit substantial irregular variations across the Ln series. It is demonstrated here that correlations of these variations with reported experimentally based atomic energies to prepare the Ln constituent for bonding reveal the nature of the bonding. Whereas some molecular characteristics are well understood in the context of highly ionic bonding, with LnX considered to be (Ln⁺)(X^-), some significant variations in BDEs are not well rationalized simply by ionization to convert Ln to Ln⁺ for bonding. Focusing here on lanthanide monofluorides LnF, a consideration of alternative Ln preparation schemes shows that a particularly good rationalization of BDEs is obtained by invoking the participation of a lanthanide 5d electron in bonding. This 5d participation could be in ionic (Ln⁺)(F^-) via π-donation from F^- 2p to empty Ln⁺ 5d orbitals or in covalent π-bonded Ln:F via polarization from Ln 5d to F 2p, with these ionic and polar covalent perspectives ultimately being equivalent. The inference of lanthanide 5d involvement suggests that the valence 4f and 6s electrons do not effectively participate in some key aspects of the bonding, presumably due to poor spatial overlap with F 2p orbitals. An extension to actinide monofluorides, AnF, assumes analogous ionic or polar covalent bonding involving a valence 6d electron and results in predictions for BDEs that include a general decrease from left to right across the series, except for a distinctive local minimum at AmF. Determining the BDE for AmF would serve to evaluate the predictions and the underlying assumption of 6d bonding. The BDE assessments/predictions for neutral monofluorides, LnF and AnF, are also applied to cationic LnF⁺ and AnF⁺, and it is noted that the approach can be directly extended to f-element monochlorides, monobromides, and monoiodides.