Theoretical Investigation of Bond Dissociation Energies of exo-Polyhedral B–H and B–F Bonds of closo-Borate Anions [BnHn−1X]2− (n = 6, 10, 12; X = H, F)

This paper reports on a theoretical investigation of the bond dissociation energies of B–H and B–F interactions of closo-borate anions [BnHn−1X]2− (n = 6, 10 and 12; X = H and F), in which homolytic and heterolytic bond breaking cases were considered, and the main trends in bond dissociation energy values were analysed. The wB97X-D3/TZVPP level of theory was applied for geometry optimisation of the molecular species under consideration. DLPNO-CCSDT/CBS single-point calculations were made to ensure an accurate estimation of the target systems’ electronic energy. The correlations between the value of the bond dissociation energy and variables such as electron density descriptors of B–H and B–F interactions and frontier orbital energies (HOMO, SOMO and LUMO) were established. © 2025 Elsevier B.V., All rights reserved.