The crystal chemistry of uranium carboxylates

Prior to the year 2000, non-aqueous uranium chemistry mainly involved metallocene and classical alkyl, amide, or alkoxide compounds as well as established carbene, imido, and oxo derivatives. Since then, there has been a resurgence of the area, and dramatic developments of supporting ligands and multiply bonded ligand types, small-molecule activation, and magnetism have been reported. This Review 1) introduces the reader to some of the specialist theories of the area, 2) covers all-important starting materials, 3) surveys contemporary ligand classes installed at uranium, including alkyl, aryl, arene, carbene, amide, imide, nitride, alkoxide, aryloxide, and oxo compounds, 4) describes advances in the area of single-molecule magnetism, and 5) summarizes the coordination and activation of small molecules, including carbon monoxide, carbon dioxide, nitric oxide, dinitrogen, white phosphorus, and alkanes.

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The Renaissance of Non-Aqueous Uranium Chemistry

Solution and solid-state structural chemistry of actinide hydrates and their hydrolysis and condensation products.

Oxalate production by fungi: significance in geomycology, biodeterioration and bioremediation

Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges

Actinide oxalates, solid state structures and applications

Lanthanides are often used as surrogates to study the properties of actinide compounds. Their behaviour is considered to be quite similar as they both possess f valence electrons and are close in size and chemical properties. This study examines the potential of using two lanthanides (neodymium and cerium) as surrogates for plutonium during the thermal decomposition of isomorphic oxalate compounds, in the trivalent oxidation state, into oxides. Thus, the thermal decomposition of neodymium, cerium and plutonium (III) oxalates are investigated by several coupled thermal analyses (TG-DTA/DSC-MS/FT-IR) and complementary characterisation techniques (XRD, UV-vis, FT-IR, SEM, carbon analyser) under both oxidizing and inert atmosphere. The thermal decomposition mechanisms determined in this study confirmed some previous results reported in the literature, among diverging propositions, while also elucidating some original mechanisms not previously considered. Calculated thermodynamic and kinetic parameters for the studied systems under both atmospheres are reported and compared with available literature data. Similarities and differences between the thermal behaviour of plutonium(III) and lanthanide(III) oxalates are outlined.

New insights on the thermal decomposition of lanthanide(III) and actinide(III) oxalates: from neodymium and cerium to plutonium

Lanthanides are often used as surrogates to study the properties of actinide compounds. Their behaviour is considered to be quite similar as they both possess f valence electrons and are close in size and chemical properties. This study examines the potential of using two lanthanides (neodymium and cerium) as surrogates for plutonium during the thermal decomposition of isomorphic oxalate compounds, in the trivalent oxidation state, into oxides. Thus, the thermal decomposition of neodymium, cerium and plutonium(III) oxalates are investigated by several coupled thermal analyses (TG–DTA/DSC–MS/FTIR) and complementary characterisation techniques [XRD, UV/Vis and FTIR spectroscopy, scanning electron microscopy (SEM), carbon analysis] under both oxidizing and inert atmospheres. The thermal decomposition mechanisms determined in this study confirmed some previously reported results, among diverging propositions, and also elucidated some original mechanisms not previously considered. The calculated thermodynamic and kinetic parameters for the studied systems under both atmospheres are reported and compared with available literature data. Similarities and differences between the thermal behaviour of plutonium(III) and lanthanide(III) oxalates are outlined.

https://hal.archives-ouvertes.fr/hal-00945784/document

Insights into the Thermal Decomposition of Lanthanide(III) and Actinide(III) Oxalates – from Neodymium and Cerium to Plutonium

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

Stéphane Grandjean

Papers

Actinide oxalates, solid state structures and applications

New insights on the thermal decomposition of lanthanide(III) and actinide(III) oxalates: from neodymium and cerium to plutonium

Insights into the Thermal Decomposition of Lanthanide(III) and Actinide(III) Oxalates – from Neodymium and Cerium to Plutonium

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

Hydrothermal synthesis and crystal structures of new uranyl oxalate hydroxides: α- and β-[(UO2)2(C2O4)(OH)2(H2O)2] and [(UO2)2(C2O4)(OH)2(H2O)2]·H2O