In an effort to further understand the oxidation state assignment and bonding in a series of uranium-arenide complexes, a combined density functional theory (DFT) and second-order multireference (CASSCF/CASPT2) study was performed. First, the ion pairing effects on the electronic structure of unsupported uranium–arenide sandwich complexes were studied. Of note, CASSCF calculations on the model complex {[U(η6-C14H10)( η4-C14H10)(μ-OMe)]2}2- show the highly polarized uranium–arenide interactions are defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3 ± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide–arenide bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects. The second family of complexes studied are mononuclear uranium bis(anthracenide) complexes where a haptotropic ring migration is observed. The bonding and oxidation states are explored and compared to that of the previously characterized dimeric complex. Finally, three homoleptic uranium-arenides are studied where spectroscopic results suggest different oxidation states for each complex.

Electronic structure of uranium–arenide complexes

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