The world's oceans contain several billion tons of uranium, albeit at a low concentration of approximately 3 parts per billion given the massive volume of the world's oceans. This can be exploited for use in nuclear energy by using polymer adsorbents that should selectively bind and extract uranyl over other metal ions. However, vanadium and iron are significant competitors for uranyl binding on the polymer adsorbents, and it is important to understand their coordination chemistry and binding to improve their selectivity for uranyl to improve the extraction efficiency. Glutaroimide-dioxime, glutaro-di(amidoxime) and similar amidoxime ligands are small molecule analogues of the chemical composition of adsorbents that are currently being investigated in order to understand how these metals complex to it. With the former, we have isolated and studied a rare non-oxido vanadium(V) complex as well as investigated the kinetics of metal binding. The binding of these ligands are being studied with different vanadium precursors to mimic different forms of natural vanadium, as well as iron and uranium to give insight into causes for observed metal selectivity. Both structural studies as well as thermodynamic binding studies are being pursued to this end to improve uranyl extraction efficiency. New ligands are also being synthesized to understand and improve selectivity and their complexes with relevant metals studied with crystallography, NMR, and other techniques.

Binding modes and thermodynamics of iron and vanadium with amidoxime ligands

253rd National Meeting (2017)

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