Solid-state actinide acid phosphites from Phosphorous acid (cas 13598-36-2) melts

Add time:09/01/2019    Source:sciencedirect.com

The reaction of UO3 and H3PO3 at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH2(CH3)2)[UO2(HPO2OH)(HPO3)]. This compound crystallizes in space group P21/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of Phosphorous acid (cas 13598-36-2) and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO2OH)4 (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO3)(HPO2OH)2(H2O)·2(H2O). α- and β-An(HPO2OH)4 crystallize in space groups C2/c and P21/n, respectively, and comprise a three-dimensional network of An4+ cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO3)(HPO2OH)2(H2O)2·(H2O) crystallizes in a layered structure in space group Pbca that is composed of An4+ cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized.

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