N. A. Budantseva

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moskva, Moscow, Russia

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Publications (96)85.44 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: A new U(VI) compound with m-hydroxybenzoic acid, HIm[(UO2)(C7H5O3)3]·2H2O, was prepared. Its structure was determined by X-ray diffraction analysis and confirmed by the visible and IR spectra. The coordination number of the U atom is 8, with the hydroxyl O atom not involved in coordination with the metal ion. The main structural constituents of the compound are [(UO2)(C7H5O3)3]− anions formed by the sixcoordinate uranyl ion and three hydroxybenzoate ions acting as bidentate ligands. The imidazolium cations participate in hydrogen bonding, linking the adjacent [(UO2)(C7H5O3)3]− anions. The compound contains water molecules of crystallization, also participating in H bonding.
    Radiochemistry 03/2014; 56(2):145-149.
  • N. A. Budantseva, M. S. Grigor’ev, A. M. Fedoseev
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    ABSTRACT: A new complex of Np(V) with the chromate ion and an organic outer-sphere guanidinium cation is isolated from an aqueous solution. Its composition and structure are determined by X-ray diffraction analysis. The structure of [C(NH2)3]3[NpO2(CrO4)2](H2O) (I) is based on anionic chains [CpO2(CrO4)2][ n 3nt- between which guanidinium cations and crystallization water molecules are localized. Coordination polyhedra of the Np atoms (pentagonal bipyramids) in the anionic chains are joined in pairs through common equatorial edges. Singularities of the electronic and IR absorption spectra of compound I are discussed.
    Russian Journal of Coordination Chemistry 04/2013; 39(4). · 0.63 Impact Factor
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    ABSTRACT: The M-O bond lengths in the lanthanide series show a well-known behaviour due to lanthanide contraction, including so-called “gadolinium break”. All three bond lengths show a good linear correlation with Shannon ionic radii for Y3+ and Ln3+ ions with coordination number 9. Nevertheless, the slopes of these dependences are different (0.957(16) for OH-groups, 0.85(2) for carboxylate groups and 1.080(17) for water molecules) and differ from unity due to a layer nature of the structures. The ionic radii for Pu3+ and Am3+ with coordination number 9 are absent in the Shannon system of ionic radii. From our data, we can propose the values 1.172 and 1.156 Å for Pu3+, and Am3+, respectively. In all crystals the structure is stabilized through extensive hydrogen bonding involving carboxylic and hydroxyl groups and water molecules.
    Russian Journal of Coordination Chemistry 03/2013; 39(3). · 0.63 Impact Factor
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    ABSTRACT: Single crystals of [Th(TMP)6(NO3)2][Th(TMP)2(NO3)5]2 (1), [Th(TMP)4(NO3)3][Th(TMP)2(NO3)5] (2), [U(DMP)3(NO3)] (3), [Np(DMP)3(NO3)] (4), and [Pu(DMP)2(NO3)2(H2O)]·H2O (5) have been synthesized and their structures have been determined by X-ray analysis. IR and optical spectra of polycrystalline compounds 3 and 4 were measured at room temperature. The Th(IV) is crystallized as two complexes with TMP molecular ligands and NO3 anions in coordination environment. The Th atoms in cationic moieties of 1 and 2 are characterized by coordination number of 10 and in the anionic moieties by coordination number of 12. Compounds of U(IV), Np(IV) and Pu(IV) were obtained with two different anions (NO3 and DMP) in coordination environment of the central atom. U(IV) and Np(IV) compounds are isostructural and the main motif of structure is made of infinite chains of [An(DMP)3(NO3)]n, twisted around hexagonal axes. In the structure of Pu(IV) the main structural motif is made of infinite chains [Pu(DMP)2(NO3)2(H2O)]n, extending along the b axis. The coordination numbers of An(IV) are equal to 8 for U and Np, and 9 for Pu. The difference in the structure and composition of formed compounds Th and U, Np, Pu could be explained by hydrolysis of TMP at the synthesis conditions.
    Radiochimica Acta 01/2013; 101(11). · 1.41 Impact Factor
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    ABSTRACT: Co-precipitation of 233UO22+, 152Eu3+, and 90Sr2+ on melanin isolated from the preparation Mikoton, a chitin—melanin glucan complex, was studied in solutions. It was shown that the degree of coprecipitation (α) of the radionuclides depended on the solution content of polymer. The maximum value of α was at least 80% for metal-ion concentration 250 mg/L and 0.8% melanin. It was hypothesized that UO22+, Eu3+, and Sr2+ were bound mainly by carboxylic and phenolic groups of melanin. The developed co-precipitation process could be recommended for isolation and concentration of radionuclides from low-salt process solutions and natural media.
    Fibre Chemistry 07/2012; 44(2). · 0.17 Impact Factor
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    ABSTRACT: The complexation of U(VI), Np(VI), and Pu(VI) and of Np(V) with 1,2,3- and 1,2,4-benzenetricarboxylic acids (BTC) in aqueous solutions was studied in wide ranges of pH and actinyl ion concentrations. The compositions of the forming hexavalent actinide complexes were determined. Their apparent stability constants β1′ depend on pH of the solution: in the pH range 2–4, logβ1′ from 2 to 4 for the complexes of U(VI), Np(VI), and Pu(VI) with 1,2,3-BTC and from 1.5 to 3.5 for the complexes with 1,2,4-BTC. For Np(V), the β1′ values are close with both acids, and at equal pH values the Np(V) complexes are less stable than the An(VI) complexes (An = U, Np, Pu). With an increase in pH from ∼3 to 6.2–6.9, logβ1′ of the Np(V) complexes increases approximately from 0.5 to 3. Solid U(VI) complexes with 1,2,3- and 1,2,4-benzenetricarboxylic acids were synthesized by the hydrothermal method, their crystal structure was determined, and the IR spectra were examined.
    Radiochemistry 04/2012; 54(2).
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    ABSTRACT: A procedure was suggested for the synthesis of Np(VII) compounds by electrochemical oxidation in acetate solutions. The conditions for preparing compounds of type MNpO4·nH2O, where M is a single-charged cation of alkali metals, ammonium, silver, guanidinium, or tetraalkylammonium, and of Np(VII) compounds with double-charged cations of alkaline-earth metals, Cu, Cd, and Zn were studied in detail. The compounds were characterized by chemical analysis and by IR and electronic spectroscopy.
    Radiochemistry 04/2012; 54(2).
  • M. S. Grigor’ev, N. A. Budantseva, A. M. Fedoseev
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    ABSTRACT: Two series of isostructural double An(IV) and guanidinium carbonates were obtained as single crystals of the formula [C(NH2)3]6[An(CO3)5] · nH2O (An = Th, U, Np, and Pu; n = 3 (I) and 4 (II)) and examined by X-ray diffraction. For the Pu(IV) complexes, a = 10.490(2) Å, b = 33.798(5) Å, c = 10.519(2) Å, β = 119.414(7)°, space group P21/c, Z = 4, R = 0.0369 (I) and a = 16.0895(18) Å, b = 13.1458(14) Å, c = 16.6951(18) Å, β = 108.116(6)°, space group C2/c, Z = 4, R = 0.0171 (II). Both series of complexes contain the anions [An(CO3)5]6−, in which the An atom is coordinated to five chelating bidenate carbonate ions. The coordination polyhedra of the An atoms are distorted bicapped square antiprisms. Within both the series, the An-O bond lengths decrease monotonically only for the sequence Th-U-Np. The average Np-O and Pu-O bond lengths in both tri- and tetrahydrates are virtually equal. The IR and electronic absorption spectra of the complexes obtained were studied. The absorption bands due to the f-f transitions experience bathochromic shifts in the spectra of the U4+ and Pu4+ carbonate complexes and hypsochromic shifts in the spectra of the Np4+ complexes.
    Russian Journal of Coordination Chemistry 01/2012; 39(1). · 0.63 Impact Factor
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    ABSTRACT: The complexes [NpO2(DMSO)5](ClO4)2 (1) and [PuO2(DMSO)5](ClO4)2 (2), isostructural to the known uranyl complex, were synthesized in the form of single crystals. Their crystallographic characteristics were determined by single crystal X-ray diffraction. The IR and electronic absorption spectra of the crystalline U(VI), Np(VI), and Pu(VI) complexes were measured and analyzed.
    Radiochemistry 12/2011; 53(6).
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    ABSTRACT: A series of isostructural oxalates of Th, U, Np, and Pu have been synthesized. The crystal structure of {C(NH(2))(3)}(4)[An(C(2)O(4))(4)]·2H(2)O comprises infinite [An(C(2)O(4))(4)](4n-) chains, guanidinium cations and water molecules. Each An atom is connected to five oxalate anions, two of which act as bridging tetradentate ligands, while the other three function as terminating bidentate ligands. Electron and IR spectra of the compounds as well as the results of thermal analysis correlate with their structure. An actinide contraction effect is demonstrated by a decrease in the An-O interatomic distances and the volumes of An atom coordination polyhedra and Voronoi-Dirichlet polyhedra. Ten-coordinate An oxalates are discussed in terms of continuous shape measures approach.
    Inorganic Chemistry 11/2011; 50(22):11481-6. · 4.79 Impact Factor
  • N. A. Budantseva, M. S. Grigor’ev, A. M. Fedoseev
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    ABSTRACT: A new Np(V) chromate complex with outer-sphere sodium cations, Na3[NpO2(CrO4)2](H2O)5 (I), was synthesized from aqueous solution. Its composition and structure were determined by single crystal X-ray diffraction. The structure of I is based on anionic chains of the composition [NpO2(CrO4)2] n 3n−, running along [010] and forming layers parallel to the (101) plane. The Na+ ions and water molecules of crystallization are arranged between the layers. The coordination polyhedra of the Np atoms (pentagonal bipyramids) are combined pairwise by sharing common equatorial edges formed by two bridging oxygen atoms of bidentate chelate-bridging CrO4 groups. The absorption spectra of I in the IR and visible ranges are presented.
    Radiochemistry 10/2011; 53(5).
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    ABSTRACT: Four new perchlorate complexes of tetravalent actinides with dimethyl sulfoxide (DMSO) molecules (An4+ = Th, U, Np, Pu) are synthesized and studied. According to the X-ray diffraction data, compounds [Th(DMSO)9](ClO4)4 · 2CH3CN (I), [U(DMSO)8](ClO4)4 · CH3CN (II), [Np(DMSO)8](ClO4)4 · CH3CN (III), and [Pu(DMSO)8](ClO4)4 · CH3CN (IV) crystallize in the triclinic crystal system (space group P1). The crystals of compounds II–IV are isostructural. The absorption spectra of the complexes in the IR and visible regions are measured. All compounds exhibit a decrease in the frequencies of stretching vibrations ν(SO) over the spectrum of free DMSO, indicating the formation of the O-bonded complexes of An4+. The optical spectra of the crystalline compounds exhibit shifts of the bands of electronic f-f transitions of the An4+ ions relative to the hydrated ions: the bathochromic shifts for the U and Np complexes and the hypsochromic shift for the Pu complex. The first coordination sphere of the actinide atoms in the studied complexes is highly stable.
    Russian Journal of Coordination Chemistry 09/2011; 37(9):701-707. · 0.63 Impact Factor
  • M. N. Sokolova, N. A. Budantseva, A. M. Fedoseev
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    ABSTRACT: The U(VI) complex with cyanoacetic acid, [UO2(H2O)2(NCCH2COO)2] (I), was synthesized from an aqueous solution, and its X-ray diffraction analysis was carried out. The crystals are orthorhombic: space group Pca2 1, a = 25.9605(7) Å, b = 6.7634(2) Å, c = 6.3398(2) Å, V = 1113.15(6) Å3 at 100 K, and Z = 4. The coordination polyhedron of the uranium atom is a distorted pentagonal bipyramid. The cations UO22+ are bound into infinite zigzag chains by the bridging carboxyl groups of one of the anions of cyanoacetic acid. The carboxyl oxygen atom of the second anion, which is not involved in coordination, and the nitrogen atoms of the cyano groups form hydrogen bonds with the coordination water molecules. The layer structure of the compound is formed through the hydrogen bonds. The absorption spectra in the visible and infrared ranges of the crystalline compound are measured and analyzed.
    Russian Journal of Coordination Chemistry 06/2011; 37(6):478-482. · 0.63 Impact Factor
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    ABSTRACT: 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.
    Radiochemistry 08/2010; 52(4):354-357.
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    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 06/2010; 32(24).
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    ABSTRACT: The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic goups, namely the aminotriacetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH3)6][M(NTA)2(H2O)]·8H2O with M=Nd, Yb and Am, and [Co(NH3)6]2K[M3(Cit)4(H2O)3]·18H2O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents.
    Comptes Rendus Chimie 06/2010; 13(6):839-848. · 1.48 Impact Factor
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    ABSTRACT: The reaction of NpO2(CH3SO3) with methylimidazole results in the formation of novel Np(V) complex with cation–cation interaction, [NpO2(MeIm)(CH3SO3)(H2O)]. The crystal structure is confirmed by IR and UV–vis spectroscopic data.
    Inorganic Chemistry Communications 05/2010; 13:679-682. · 2.06 Impact Factor
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    ABSTRACT: Mixed valence U(VI)/U(IV) compound with organic anionic ligand bridging uranium atoms in different oxidation states was synthesized at room temperature. Coordination polyhedron of U(VI) atom is a pentagonal bipyramide whose equatorial positions are occupied by nitrogen and two oxygen atoms of one DPA2− anion, oxygen atom of another DPA2− anion and a water molecule. Second uranium atom U(IV) is surrounded by three DPA2− anions, one of which is tetradentate and acts as bridging ligand connecting metal centers, while other two DPA2− anions are tridentate. The crystal structure is confirmed by UV–vis and IR spectroscopic data.
    Inorganic Chemistry Communications 05/2010; 13:577-579. · 2.06 Impact Factor
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    ABSTRACT: Sorption of Th, uranyl, Am, Fe, and Al ions from nitric acid solutions on various phosphorus-containing ion-exchange materials (organic ion-exchange resins, SE-UPO solid extractant) was studied. The highest selectivity to quadruple-charged metal cations is exhibited by S-957 cation exchanger (Purolite) with phosphonic and sulfonic acid groups. The capacity of this resin for Th is essentially independent of the HNO3 concentration in the range 1–7 M and amounts to 80–95 mg ml−1. The uranyl, Am, Fe, and Al ions are sorbed on S-957 resin considerably worse than Th. The internal diffusion coefficient of Th4+ ions in S-957 resin from 3 M HNO3 was determined to be (5.3 ± 0.5) × 10−13 m2 s−1. The IR spectra of S-957 resin in the hydrogen and thorium forms were recorded. S-957 resin shows promise for selective recovery of tetravalent actinides from multicomponent nitric acid-salt solutions.
    Radiochemistry 02/2010; 52(1):71-75.
  • M. S. Grigor’ev, N. A. Budantseva, A. M. Fedoseev
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    ABSTRACT: The single crystals of the Np(V) complex (NH4)[NpO2(CO3)] (I) were synthesized and studied by X-ray diffraction. At 100 K, the crystals are hexagonal, space group P63 μmc, a = 5.0734(1) Å, c = 10.9191(2) Å, V= 243.399(11) Å3, Z = 2, ρ(calcd) = 4.735 g/cm3. The absorption spectra of a crystal of I in the visible and infrared ranges were measured.
    Russian Journal of Coordination Chemistry 01/2010; 36(2):157-160. · 0.63 Impact Factor

Publication Stats

214 Citations
85.44 Total Impact Points

Institutions

  • 2007–2013
    • A. N. Frumkin Institute of Physical Chemistry and Electrochemistry
      Moskva, Moscow, Russia
  • 1998–2013
    • Russian Academy of Sciences
      • • A.N. Frumkin Institute of Physical chemistry and Electrochemistry
      • • Institute of Chemistry
      Moskva, Moscow, Russia
  • 2002
    • Pacific Northwest National Laboratory
      Richland, Washington, United States