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Title: Directed synthesis of crystalline plutonium (III) and (IV) oxalates: accessing redox-controlled separations in acidic solutions

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic900344u· OSTI ID:956410
 [1];  [1];  [1];  [1];  [1]
  1. Los Alamos National Laboratory
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Both binary and ternary solid complexes of Pu(III) and Pu(IV) oxalates have been previously reported in the literature. However, uncertainties regarding the coordination chemistry and the extent of hydration of some compounds remain mainly because of the absence of any crystallographic characterization. Single crystals of hydrated oxalates of Pu(III), Pu{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}{center_dot}3H{sub 2}O (I) and Pu(IV), KPu(C{sub 2}O{sub 4}){sub 2}(OH){center_dot}2.5H{sub 2}O (II), were synthesized under moderate hydrothermal conditions and characterized by single crystal X-ray diffraction studies. Compounds I and II are the first plutonium(III) or (IV) oxalate compounds to be structurally characterized via single crystal X-ray diffraction studies. Crystallographic data for I: monoclinic, space group P21/c, a = 11.246(3) A, b = 9.610(3) A, c = 10.315(3) A, Z = 4 and II: monoclinic, space group C2/c, a = 23.234(14) A, b = 7.502(4) A, c = 13.029(7) A, Z = 8.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC52-06NA25396
OSTI ID:
956410
Report Number(s):
LA-UR-09-00848; LA-UR-09-848; INOCAJ; TRN: US1004053
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry; ISSN 0020-1669
Country of Publication:
United States
Language:
English

References (39)

A new series of mixed oxalates MM′(C2O4)3(H2O)3·nH2O (M=Cd, Hg, Pb; M′=Zr, Hf) based on eight-fold coordinated metals: Synthesis, crystal structure from single-crystal and powder diffraction data and thermal behaviour journal November 2007
The unit cells of some americium(III)—salts with organic anions journal October 1967
Synthesis, crystal structure of Gd(H2O)(C2O4)2 · NH4 and of La(C2O4)2 · NH4. Characterization of the Ln(H2O)(C2O4)2 · NH4 with Ln=Eu…Yb journal March 2001
Adaptable coordination of U(IV) in the 2D-(4,4) uranium oxalate network: From 8 to 10 coordinations in the uranium (IV) oxalate hydrates journal August 2008
A neodymium(III)–ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)]·H2O journal September 2002
Higher Order Speciation Effects on Plutonium L 3 X-ray Absorption Near Edge Spectra journal January 2004
Compounds Exhibiting Coördination Number Eight. The Potassium Tetraoxalatometallates of Zirconium(IV), Hafnium(IV), Thorium(IV), and Uranium(IV) journal February 1962
Synthesis and structure of [Ce2(H2O)3](C2O4)2.5(H3C2O3) and Ce2(C2O4)(H3C2O3)4: The latter structure presents an interesting new framework, with 2-fold interpenetration journal April 2005
Preparation, sintering and leaching of optimized uranium thorium dioxides journal March 2009
Synthesis of New Crystalline Pu(V) Compounds from Solutions: V. Crystal Structure of [Co(NH3)6][PuO2(C2O4)2] · 3H2O journal September 2005
The crystal structure of tetrapotassium tetraoxalatothorium(IV) tetrahydrate, K4Th(C2O4)4.4H2O journal May 1975
Precipitation of plutonium oxalate from homogeneous solutions journal July 1986
Synthesis and crystal structure of [Tb4(H2O)2](C2O4)2(C5H6O4)4 journal October 2000
Synthesis of new mixed actinides oxalates as precursors of actinides oxide solid solutions journal October 2007
Reaction mechanisms of the thermal conversion of Pu(IV) oxalate into plutonium oxide journal October 2007
Thermal decomposition of plutonium oxalates journal October 1963
The effect of the lanthanoid contraction on the nonaaqualanthanoid(III) tris(trifluoromethanesulfonates) journal August 1988
Synthesis and crystal structure of La(H2O)(C2O4)2·(CN3H6) and of [Nd(H2O)]2(C2O4)4·(NH4)(CN3H6) journal September 2002
Two New Families of Lanthanide Mixed-Ligand Complexes, Oxalate–Carbonate and Oxalate–Formate: Synthesis and Structure of [Ce(H2O)]2(C2O4)2(CO3)·2.5 H2O and Ce(C2O4)(HCO2) journal December 1996
Crystal growth and structure of La2(C2O4)3 9.5H2O journal April 1988
Synthesis and crystal structure of [Nd(H2O)2]2(C2O4)3 journal January 2003
Synthesis and characterization of mixed An(IV)An(III) oxalates (An(IV)=Th, Np, U or Pu and An(III)=Pu or Am) journal February 2008
Single Crystal and Solution Complex Structure of Nd(CO3)45-. The First Characterization of a Mononuclear Lanthanide(III) Carbonato Complex journal February 2000
X-ray powder crystallographic data on plutonium and other oxalates—II journal January 1965
U(IV)/Ln(III) unexpected mixed site in polymetallic oxalato complexes. Part I. Substitution of Ln(III) for U(IV) from the new oxalate (NH4)2U2(C2O4)5·0.7H2O journal October 2005
The thermal decomposition of curium(III) oxalate IO-hydrate journal July 1968
U(IV)/Ln(III) mixed site in polymetallic oxalato complexes. Part III: Structure of Na[Yb(C2O4)2(H2O)]·3H2O and the derived quadratic series (NH4+)1−x[Ln1−xUx (C2O4)2(H2O)]·(3+x) H2O, Ln=Y, Pr–Sm, Gd, Tb journal December 2006
Structure of lanthanum chloride oxalate trihydrate journal June 1990
Hydrothermal synthesis, crystal structure and characterizations of a lanthanum(III) sulfate oxalate with a 3D network structure journal January 2004
High-Yield Synthesis and Single-Crystal X-ray Structure of a Plutonium(III) Aquo Complex:  [Pu(H 2 O) 9 ][CF 3 SO 3 ] 3 journal June 2001
A Novel Methodology for Processing of Plutonium-Bearing Waste as Ammonium Plutonium(III)-Oxalate journal September 2005
Synthesis and crystal structure of three-dimensional open-framework lanthanide oxalates containing either the guanidinium or tetramethylammonium ions journal December 2004
The crystal structure of some lanthanide oxalate decahydrates, Ln2(C2O4)3·10H2O, with Ln = La, Ce, Pr, and Nd journal April 1969
Structural Studies on the Rare Earth Carboxylates. 5. Crystal and Molecular Structure of Neodymium(III) Oxalate 10.5-Hydrate. journal January 1970
On the Crystal Structure of Neodymium Oxalate. journal January 1968
X-ray powder crystallographic data on plutonium and other oxalates—I journal January 1965
Crystal structure of lanthanum(III) oxalate decahydrate journal April 1991
Crystal structure and characterization of [La(H2O)]2(C2O4)(C4H4O5)2 journal May 2000
The thermal decomposition of americium (III) oxalate journal October 1958

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
HYDRATION
MONOCRYSTALS
OXALATES
PLUTONIUM COMPLEXES
SYNTHESIS
CRYSTAL STRUCTURE