The Counterintuitive Relationship between Orbital Energy, Orbital Overlap, and Bond Covalency in CeF₆^2- and CeCl₆²

The 4f orbitals of Ce(IV) have shown appreciably enhanced covalent mixing with ligand orbitals relative to those of Ce(III). Here, X-ray spectroscopy, magnetic susceptibility measurements, and theoretical methods are used to investigate 4f covalency in CeF₆^2- and CeCl₆^2-. These techniques show covalent mixing between Ce 4f and F 2p orbitals to be about 25% less than mixing between Ce 4f and Cl 3p orbitals, placing CeF₆^2- among the most ionic Ce(IV) compounds to-date. However, ligand field analysis using the experimental data shows significantly higher 4f orbital overlap with the F 2p orbitals compared to the Cl 3p. This result is counterintuitive since the Ce-F bonds display less 4f covalency despite their higher orbital overlap, and greater overlap is traditionally associated with enhanced bond covalency. The weaker covalency is attributed to the large energy gap between Ce 4f and F 2p orbitals strongly counteracting the higher orbital overlap. These results highlight that only a concerted consideration of both atomic orbital overlap and energy matching in f-element systems leads to an accurate picture of their bonding.