Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-Donating and -Withdrawing Groups

Abstract

Neptunium makes up the largest percentage of minor actinides found in spent nuclear fuel, yet separations of this element have proven difficult due to its rich redox chemistry. Developing new reprocessing techniques should rely on understanding how to control the Np oxidation state and its interactions with different ligands. Designing new ligands for separations requires understanding how to properly tune a system toward a desired trait through functionalization. Emerging technologies for minor actinide separations focus on ligands containing carboxylate or pyridine functional groups, which are desirable due to their high degree of functionalization. Here, we use DFT calculations to study the interactions of carboxylate and polypyridine ligands with the neptunyl cation [Np(V/VI)O2]+/2+. A systematic study is performed by varying the electronic properties of the carboxylate and polypyridine ligands through the inclusion of different electron-withdrawing and electron-donating R groups. We focus on how these groups can affect geometric properties, electronic structure, and bonding characterization as a function of the metal oxidation state and ligand character and discuss how these factors can play a role in neptunium ligand design principles.

Pyridine Diphosphonate Ligand for Stabilization of Tetravalent Uranium and Neptunium in Aqueous Medium under Aerobic Conditions

“…This complexation behavior of the penta- and hexavalent actinyl ions can be explained from their respective molecular orbital diagrams (Figure ). The frontier orbitals of the actinyl ions are mainly metal cantered “5f”-based orbitals though the symmetry of the lowest unoccupied molecular orbitals (LUMO) changes as the number of “f” electrons varies.…”