Probing Actinide Covalency using NMR Spectroscopy and DFT Calculations

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AREAS: SYNTHETIC COORDINATION CHEMISTRY, COMPUTATIONAL AND THEORETICAL CHEMISTRY, ANALYTICAL SCIENCE A central aim of actinide science is to better quantify the covalency of actinide-ligand bonding, and to relate this to elements across the rest of the periodic table. Experimentally probing the covalency of actinide bonding is challenging; there are few experimental measures of covalency. Nevertheless, with novel molecules, that display traits which remain hidden in simple systems close to thermodynamic sinks, we can use NMR spectroscopy to probe actinide-covalency experimentally.Previously (Nat. Commun. 2021, 12, article number 5649), we showed that the covalency of a uranium-nitride triple bond could be probed using 15N NMR spectroscopy (solution and solid-state MAS), revealing unprecedented NMR spectroscopic properties and actinide covalency. The marriage of experimental and computational methods was essential to this success.In this project, you will prepare a range of existing and novel new actinide complexes, sometimes with isotopic labels, and, in addition to characterising them with the usual range of analytical techniques, will probe the covalency of the key actinide-ligand linkages with detailed NMR and computational studies to quantify the covalency. Our overall aim is, through the study of various related complexes and NMR nuclei, to build our understanding of actinide covalency.