Synthesis and properties of actinide dimolybdate complexes M<Subscript>2</Subscript>[AnO<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>]·H<Subscript>2</Subscript>O (M = Rb,Cs; An = Np,Pu)

New Np(VI) and Pu(VI) dimolybdates Rb₂NpO₂(MoO₄)₂·H₂O (I), Cs₂NpO₂(MoO₄)₂·H₂O (II), Cs₂PuO₂(MoO₄)₂·H₂O (III), and Rb₂PuO₂(MoO₄)₂·H₂O (IV) were synthesized under hydrothermal conditions. The crystal structures of the compounds were determined, and their absorption spectra in the UV, visible, and IR ranges were measured. The compounds crystallize in the monoclinic system. Their crystal structure is based on [AnO₂(MoO₄)₂]_n^2n– anionic layers (An = Np, Pu) formed by (AnO₂)O₅ pentagonal bipyramids and MoO₄ tetrahedra, sharing common vertices. Each An atom in the layer is bonded to other five An atoms via MoO₄ tetrahedra with the formation of a 4343² network. The effect of the ionic radius of the outer-sphere cation on the parameters of the crystal structure and features of the absorption spectra is discussed.     

Selective Recovery of Chromium from Precipitates Containing d Elements and Actinides: I. Effect of O2

Oxidation of Cr(III) hydroxides, double Fe(III)-Cr(III) hydroxides, and some examples of spinel phases NiCr₂O₄ and Fe(Cr,Fe)₂O₄ in alkaline suspensions (0.2-0.5 M NaOH) under the action of air and pure oxygen (1-3 atm) was studied. The reaction rate increases with increasing concentration of alkali, temperature, and oxygen pressure. Under these conditions, Pu(IV) sorbed on chromium hydroxides is not oxidized with oxygen and remains in the precipitate.     

Synthesis and Structure of U(VI), Np(VI), and Pu(VI) 2-Fluorobenzoates

The compounds NH₄[AnO₂(C₆H₄FCOO₃], where An = U (I), Np (II), or Pu (III), CgH₄COO^? is the 2-fluorobenzoate anion, were synthesized and studied by single crystal X-ray diffraction. Compounds I–III are isostructural and crystallize in the cubic system, space group P2₁3, Z = 4. The main structural units of I–III are mononuclear complexes [AnO₂(C₆H₄COO)₃]^? belonging to crystal-chemical group AB₃¹ (A = AnO₂²⁺, B⁰¹ = C₆H₄FCOO^?). The actinide contraction in the structures of I–III is manifested in a regular decrease in the lengths of the An=0 bonds in the AnO₂²⁺ cations and in the volumes of the Voronoi-Dirichlet polyhedra (VDPs) of the An atoms in the series U-Np-Pu. The intermolecular interactions in crystal structures of I–III were analyzed by the method of molecular VDPs.

     

Interaction of methanesulfonic acid with actinide ions. The new complexes HImid[Np(C2O4)(CH3SO3)3(H2O)2], [NpO2(Terpy)(CH3SO3)(H2O)]·2H2O, and [UO2(CH3SO3)2(H2O)]

Complexation of methanesulfonic acid with Np(IV), Np(V), and U(VI) ions in aqueous solutions was studied. New crystalline compounds HImid[Np(C₂O₄)(CH₃SO₃)₃(H₂O)₂] (I), [NpO₂(Terpy)(CH₃SO₃)·(H₂O)]·2H₂O (II), and [UO₂(CH₃SO₃)₂(H₂O)] (III) were isolated. The absorption spectra of all the compounds in the IR, visible, and UV ranges were examined. The relationship between the composition, crystal structure, and IR and electronic absorption spectra of the complexes is discussed. Original Russian Text ? G.B. Andreev, N.A. Budantseva, I.G. Tananaev, B.F. Myasoedov, 2009, published in Radiokhimiya, 2009, vol. 51, no. 3, pp. 197–201.     

Interaction of Np(V), (VI), and (VII) with Aluminosilicates in Alkaline Medium

The behavior of Np in higher oxidation states in alkaline solution containing silicate and aluminate ions was studied. In formation of a crystalline aluminosilicate in a solution, Np(V), (VI), and (VII) are not incorporated into its crystal structure but hamper formation of the solid phase. The possibility of sorption of Np on various aluminosilicates is primarily governed by its oxidation state. Np(V) and Np(VII) are not sorbed from strong alkali. Np(VI) is retained by aluminosilicate materials to various extents depending on the surface characteristics and surface area of these materials. On heating, the degree of Np(VI) sorption decreases, which suggests the physical nature of the process.     

Interaction of transuranium elements with biologically relevant ligands. Synthesis,crystal structure,IR and electronic spectra of neptunium glycolate [NpO2(C2O3H3)(Bipy)] · 2.5H2O

As a result of Np(V) glycolate reaction with 2,2′-bipyridyl, the novel coordination polymer [NpO₂(C₂O₃H₃)(Bipy)] · 2.5H₂O was formed. The structure consists of infinite chains of [NpO₂(C₂O₃H₃)(Bipy)] and water molecules. The crystal structure is confirmed by IR and UV–vis spectroscopic data. This complex is the first example of An glycolate with neutral molecular ligand.     

Tetramethylammonium Neptunium(IV) Isothiocyanate [N(CH3)4]4[Np(NCS)8]

A new Np(IV) complex, [N(CH₃)₄]₄[Np(NCS)₈], was prepared. Its crystal structure was determined, and the absorption spectra in the IR and near IR ranges were measured. Crystal data: a = 27.280(6), b = 12.288(3), c = 13.493(3) Å, space group Pna2₁, Z = 4, V = 4523(2) A³, R = 0.044, wR(F ²) = 0.091. The crystal structure of the compound consists of [Np(NCS)₈]^{4 -} anions and N(CH₃)₄ ⁺ cations. The coordination polyhedron of the Np atom is a distorted tetragonal antiprism formed by the nitrogen atoms of eight NCS^- ions.     

Synthesis,crystal structure,and spectral properties of a complex of U(VI) with <Emphasis Type="Italic">m</Emphasis>-hydroxybenzoic acid

A new complex compound of U(VI) with m-hydroxybenzoic acid, K[(UO₂)(C₇H₅O₃)₃]·5H₂O, was prepared and characterized. A single crystal X-ray diffraction study showed that the coordination polyhedron of the U atom is a hexagonal bipyramid whose equatorial plane is formed by the O atoms of carboxy groups of three anions of m-hydroxybenzoic acid. The K atoms act as outer-sphere cations linking the adjacent anions [UO₂(C₇H₅O₃)₃]⁻ into neutral dimers {[UO₂(C₇H₅O₃)₃]K(H₂O)₃}₂. The structure also contains water molecules of crystallization, retained by hydrogen bonds.     

Interaction of Pu(VI) with Aluminosilicate in Alkaline Solution

Behavior of Pu(VI) in the course of crystallization of aluminosilicate in 2 and 3 M NaOH was studied. Plutonium(VI) inhibits aluminosilicate crystallization. At the Al : Si : Pu molar ratio of 10 : 40 : 2 in the initial mixture, only a minor amount of the X-ray amorphous phase is formed. Partial sorption of Pu(VI) on the aluminosilicate precipitate depends on the alkali concentration in the solution. As determined by spectrophotometry, only neutral and low-charged Pu(VI) hydroxo complexes are sorbed on the aluminosilicate; anionic complexes like [PuO₂(OH)₄]^{2 -} formed in more alkaline solutions are not sorbed. Plutonium(IV) formed by reduction of Pu(VI) is sorbed on aluminosilicate from 3 M NaOH.     

Synthesis,crystal structure,and properties of new actinide(VI) arsenates (H<Subscript>3</Subscript>O)[(AnO<Subscript>2</Subscript>)(AsO<Subscript>4</Subscript>)]·3H<Subscript>2</Subscript>O (An = U,Np, Pu)

Previously unknown arsenates of hexavalent U, Np, and Pu, (H₃O)[(UO₂)(AsO₄)]·3H₂O (I), (H₃O)· [(NpO₂)(AsO₄)]·3H₂O (II), and (H₃O)[(PuO₂)(AsO₄)]·3H₂O (III), were synthesized under hydrothermal conditions. The crystal structure of the compounds was determined, and their absorption spectra were measured. The compounds crystallize in tetragonal space group P4/nmm.