Speciation is critical to understanding the overall chemical behavior of metal ions. For the actinides, efforts to elucidate the metal complexes that form under a given set of conditions are motivated by their importance to waste management, separations, and environmental transport. Hydrolysis chemistry, oxidation reactions, and metal-ligand complexation are several factors known to impact speciation. Ligand complexation, in particular, has been used to “trap” hydrolysis products, stabilize polynuclear clusters, or otherwise direct the formation of unique structural units. With this in mind, our group has been examining the structural chemistry of An(IV) complexes and extended networks that form in the presence of carboxylate donor ligands. Our interest broadly lies in understanding how functionalization of ligands containing similar oxygen donor groups affects the assembly and relative stability of actinide structural units. In this work, we investigated U(IV) complexation by 2-furoic acid. The effects of various synthetic parameters, including the solvent system, metal to ligand ratios, and temperature, on the solid state structural chemistry were examined. Five compounds were observed as a function of reaction conditions, ranging in nuclearity from tetrameric units to a U<sub>38</sub> cluster and ranging in dimensionality from isolated molecular units to extended 1-dimensional chains. Presented here will be an examination of the various structural units that form from complexation of U(IV) by 2-furoate and a discussion of the synthetic conditions over which each phase is isolated.

Structural chemistry of uranium(IV)-furoate complexes

2019 Fall National Meeting

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