Emergence of the Structure-Directing Role of f-Orbital Overlap-Driven Covalency

FEUDAL (f’s essentially unaffected, d’s accommodate ligands) is a longstanding bonding model in actinide chemistry, in which metal-ligand binding uses 6d-orbitals, with the 5f remaining nonbonding. The inverse-trans-influence (ITI) is a case where the model may break down, and it has been suggested that ionic and covalent effects work synergistically in the ITI. Here, we report an experimentally grounded computational study that quantitatively explores the ITI, and in particular the structure-directing role of f-orbital covalency. Strong donor ligands generate a cis-liganddirecting electrostatic potential (ESP) at the metal centre. When f-orbital participation, via overlapdriven covalency, becomes dominant via short actinide-element distances, this ionic ESP effect is overcome, favouring a trans-ligand-directed geometry. This study contradicts the accepted ITI paradigm in that here ionic and covalent effects work against each other, and suggests a clearly non-FEUDAL, structure-directing role for the f-orbitals.