Involvement of 5f Orbitals in the Covalent Bonding between the Uranyl Ion and Trialkyl Phosphine Oxide: Unraveled by Oxygen K-Edge X-ray Absorption Spectroscopy and Density Functional Theory

Monodentate organophosphorus ligands have been used for the extraction of the uranyl ion (UO22+) for over half a century and have exhibited exceptional extractability and selectivity toward the uranyl ion due to the presence of the phosphoryl group (O=P). Tributyl phosphate (TBP) is the extractant of the world-renowned PUREX process, which selectively recovers uranium from spent nuclear fuel. Trialkyl phosphine oxide (TRPO shows extractability toward the uranyl ion that far exceeds that for other metal ions, and it has been used in the TRPO process. To date, however, the mechanism of the high affinity of the phosphoryl group for UO22+ remains elusive. We herein investigate the bonding covalency in a series of complexes of UO22+ with TRPO by oxygen K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory (DFT) calculations. Four TRPO ligands with different R substituents are examined in this work, for which both the ligands and their uranyl complexes are crystallized and investigated. The study of the electronic structure of the TRPO ligands reveals that the two TRPO molecules, irrespective of their substituents, can engage in sigma- and pi-type interactions with U Sf and 6d orbitals in the UO2Cl2 (TRPO)(2) complexes. Although both the axial (O-yl) and equatorial (O-eq) oxygen atoms in the UO2Cl2 (TRPO)(2) complexes contribute to the X-ray absorption, the first pre-edge feature in the O K-edge XAS with a small intensity is exclusively contributed by O-eq and is assigned to the transition from O-eq is orbitals to the unoccupied molecular orbitals of 1b(1u) + 1b(2u) + 1b(3u) symmetries resulting from the sigma- and pi-type mixing between U Sf and O-eq 2p orbitals. The small intensity in the experimental spectra is consistent with the small amount of O-eq 2p character in these orbitals for the four UO2Cl2 (TRPO)(2) complexes as obtained by Mulliken population analysis. The DFT calculations demonstrate that the U 6d orbitals are also involved in the U-TRPO bonding interactions in the UO2Cl2 (TRPO)(2) complexes. The covalent bonding interactions between TRPO and UO22+, especially the contributions from U 5f orbitals, while appearing to be small, are sufficiently responsible for the exceptional extractability and selectivity of monodentate organophosphorus ligands for the uranyl ion. Our results provide valuable insight into the fundamental actinide chemistry and are expected to directly guide actinide separation schemes needed for the development of advanced nuclear fuel cycle technologies.