Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U-Furoate Phase Formation |
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| Authors: | Dr Nicole A Vanagas Dr Robert F Higgins Jennifer N Wacker Dane Romar C Asuigui Evan Warzecha Dr Stosh A Kozimor Prof Sarah L Stoll Prof Eric J Schelter Dr Jeffery A Bertke Prof Karah E Knope |
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| Institution: | 1. Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C., 20057 United States;2. P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania, 19104 United States;3. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida, 32306 United States;4. Los Alamos National Laboratory, Los Alamos, New Mexico, 87545 United States |
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| Abstract: | Uranium(IV) complexation by 2-furoic acid (2-FA) was examined to better understand the effects of ligand identity and reaction conditions on species formation and stability. Five compounds were isolated: UCl2(2-FA)2(H2O)2]n ( 1 ), U4Cl10O2(THF)6(2-FA)2] ? 2 THF ( 2 ), U6O4(OH)4(H2O)3(2-FA)12] ? 7 THF ? H2O ( 3 ), U6O4(OH)4(H2O)2(2-FA)12] ? 8.76 H2O ( 4 ), and U38Cl42O54(OH)2(H2O)20] ? m H2O ? n THF ( 5 ). The structures were determined by single-crystal X-ray diffraction and further characterized by Raman, IR, and optical absorption spectroscopy. The thermal stability and magnetic behavior of the compounds were also examined. Variations in the synthetic conditions led to notable differences in the structural units observed in the solid state. At low H2O/THF ratios, a tetranuclear oxo-bridged U4O2] core was isolated. Aging of this solution resulted in the formation a U38 oxo cluster capped by chloro and water ligands. However, at increasing water concentrations only hexanuclear units were observed. In all cases, at temperatures of 100–120 °C, UO2 nanoparticles formed. |
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| Keywords: | 2-furoic acid crystallization hydrolysis uranium X-ray diffraction |
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