Phosphonoacetate as a Ligand for Constructing Layered and Framework Alkali Metal Uranyl Compounds

The hydrothermal reactions of KCl, RbCl, CsOH, and CsCl with phosphonoacetic acid and uranium trioxide at 180 °C for three to five days results in the formation of five different crystalline uranyl carboxyphosphonates, K[(UO2)2(PO3CH2CO2)(PO3CH2CO2H)(H2O)]·H2O, Rb[(UO2)2(PO3CH2CO2)(PO3CH2CO2H)(H2O)]...

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Bibliographic Details
Published in:Inorganic chemistry 2009-12, Vol.48 (23), p.11079-11084
Main Authors: Alsobrook, Andrea N, Albrecht-Schmitt, Thomas E
Format: Article
Language:English
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Summary:The hydrothermal reactions of KCl, RbCl, CsOH, and CsCl with phosphonoacetic acid and uranium trioxide at 180 °C for three to five days results in the formation of five different crystalline uranyl carboxyphosphonates, K[(UO2)2(PO3CH2CO2)(PO3CH2CO2H)(H2O)]·H2O, Rb[(UO2)2(PO3CH2CO2)(PO3CH2CO2H)(H2O)]·H2O, Cs[(UO2)2(PO3CH2CO2)(PO3CH2CO2H)(H2O)]·H2O, Cs[(UO2)(PO3CH2CO2)], and Cs3[(UO2)4(PO3CH2O2)2(PO3CH2CO2H0.5)2]·nH2O, respectively. In all compounds, the UO2 2+ moieties are bound by phosphonate and carboxylate forming pentagonal bipyramidal environments around the uranium centers. At low pH, some of the carboxylate portions of the phosphonoacetate are protonated. The addition of hydroxide removes these protons, and a different structure is adopted. In contrast to all other uranyl carboxyphosphonates, Cs3[(UO2)4(PO3CH2O2)2(PO3CH2CO2H0.5)2]·nH2O adopts a three-dimensional network structure with large channels along the c axis that house the Cs+ cations.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic9014493