N. A. Budantseva

The A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Moskva, Moscow, Russia

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Publications (117)83.18 Total impact

  • G. B. Andreev · N. A. Budantseva · A. M. Fedoseev
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    ABSTRACT: The new complexes [PuO2CrO4(urea)3] (1) and [PuO2CrO4(urea)2] (2) were isolated from aqueous solutions. Their composition and structure were determined by single crystal X-ray diffraction analysis. Compound 1 has a chain structure, with each Pu atom coordinated by the O atoms of three urea molecules and two bidentate chromate ions. In the structure of 2, each Pu is bonded to the O atoms of two urea molecules and three tridentate chromate ions, each of which is bonded to three Pu atoms. The geometric characteristics of the structures differ appreciably, primarily in the orientation of urea molecules in the space. The electronic and IR absorption spectra of complexes 1 and 2 and of uranium and neptunium analogs of 2, [UO2CrO4(urea)2] and [NpO2CrO4(urea)2], also synthesized in the study, were measured.
    No preview · Article · Sep 2015 · Radiochemistry
  • N. A. Budantseva · M. S. Grigor’ev · A. M. Fedoseev
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    ABSTRACT: Previously unknown Np(V) compounds with γ-octamolybdate anions are reported. A series of complexes of the general composition M6[(NpO2)2(Mo8O28)]·2H2O (M = NH4, K, Rb, Cs, Tl) were synthesized by the hydrothermal method from aqueous solutions. The composition and crystal structure of the compounds were determined by single crystal X-ray diffraction. All the compounds contain the NpO2+ dioxocations, (Mo8O28)8− anions, M+ cations, and water molecules of crystallization. The Np atoms have the pentagonal bipyramidal oxygen surrounding, with five O atoms of three different octamolybdate ions arranged in the equatorial plane of the dioxocation. The complexes with the NH4, K, Rb, and Tl cations are isostructural (space group P \(\bar 1\)), whereas the complex with the Cs cation crystallizes in another space group (P21/n). The structure of the centrosymmetric octamolybdate ions (Mo8O28)8− is similar in all the compounds. The oxygen surrounding of the outer-sphere cations is characterized by a large scatter of the interatomic distances, and both the main and additional coordination numbers of the cations can be considered. The electronic and vibrational absorption spectra of the synthesized Np(V) octamolybdate complexes were measured and analyzed. The influence of the structural features of the complexes and of the kind of the outer-sphere cation on the spectral pattern is discussed.
    No preview · Article · May 2015 · Radiochemistry
  • I. A. Charushnikova · N. A. Budantseva · A. M. Fedoseev
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    ABSTRACT: The structure and spectra of the Np(V) terephthalate [C(NH2)3]3[NpO2(C6H4(COO)2)2]·5H2O (I) and An(VI) terephthalates [AnO2(C6H4(COO)2)] (II), where An = U, Np, or Pu, were studied. The crystal structure of I is build of NpO2+ cations and terephthalate anions linked with each other in infinite anionic chains [NpO2(C6H4(COO)2)2]n3−, with the water molecules and guanidinium cations arranged between them. The Np atom has the coordination surrounding in the form of a hexagonal bipyramid whose equatorial plane is formed by the O atoms of three [C6H4(COO)2]2− anions. There are two independent [C6H4(COO)2]2− anions in the structure. One of them is bidentate chelating, and the other is chelating and bridging, with both of its carboxylate groups bonded to the NpO2+ cations in the anionic chains in the bidentate fashion. Five crystallographically independent water molecules are localized in the structure of I. Together with the [C(NH2)3]+ cations, these water molecules form a three-dimensional system of hydrogen bonds. The crystal structure of II is built of neutral [AnO2(C6H4(COO)2)]n layers formed by the AnO22+ cations and terephthalate anions. The An(VI) atom has the coordination surrounding in the form of a tetragonal bipyramid whose equatorial plane is formed by the O atoms of four [C6H4(COO)2]2− anions. The IR and electronic absorption spectra of the compounds are presented.
    No preview · Article · May 2015 · Radiochemistry
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    ABSTRACT: New U(VI) o-methoxybenzoate compounds of the compositions ImH[UO2(C8H7O3)3]·H2O and 1-MeImH[UO2(C8H7O3)3]·H2O (Im is imidazole, 1-MeIm is 1-methylimidazole) were synthesized. Their structure was determined by single crystal X-ray diffraction and confirmed by visible and IR spectroscopy. The compounds are isostructural and consist of [UO2(C8H7O3)3]− anions formed by six-coordinate uranyl ion and three methoxybenzoate ions acting as bidentate ligands, and also of imidazolium or methylimidazolium cations and water molecules.
    No preview · Article · Mar 2015 · Radiochemistry
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    A. M. Fedosseev · G. B. Andreev · N. A. Budantseva · J. C. Krupa
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    ABSTRACT: Nitrogen-bearing ligands have received a lot of attention focused primarily on liquid-liquid extraction and separation of lanthanides and actinides. To modelise the complexation mechanism and to understand more deeply the electronic and thermodynamic properties of complexes formed in solution, compound structural data are needed. The present work deals with the synthesis and the crystal structure of three Np(V) compounds: [(NpO2)(NO3)Tpy(H2O)], [(NpO2){4-(OOC)NC5H4}Tpy(H2O)]2H2O formed with terpyridine (Tpy) and [NpO2(2-(OOC)NC5H4)(H2O)2], a new Np(V) complex formed with picolinate-ion. Far-IR spectroscopic properties are investigated and discussed in terms of deformation vibrations in the neptunyl groupings
    Preview · Article · Aug 2014 · Journal of Nuclear Science and Technology
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    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.
    No preview · Article · Mar 2014 · Radiochemistry
  • Nina A. Budantseva · Mikhail S. Grigoriev · Aleksandr M. Fedosseev
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    ABSTRACT: Single crystals of the two new compounds [(AmO2)-O-v(dipy)OOCCH3(H2O)] (I) andCs(2) [((AmO2)-O-VI)(2) (SO4)(3)] (II) have been synthesized and their structures have been determined by X-ray structural analysis. IR and optical spectra of polycrystalline compounds I and II were measured and interpreted. The structure I is formed by electroneutral complexes [ (AmO2)-O-v (dipy) OOCCH3 (H2O)], in which dioxocations AmO2+ are coordinated by two N atoms of a bidentate-chelating dipy ligand, two O atoms of a bidentate-chelating acetate anion and one O atom of water molecule. Due to a different nature of ligands, the distances and bond angles in the equatorial plane of AmO2+ have a significant spread. The structure II is built of interlaced anionic and cationic layers. Anionic layers [((AmO2)-O-VI)(2)(SO4)(3)](n)(2n) contain AmO22+ groups and two types of SO42-anions: tridentate-and tetradentatebridging. Each AmO22+ is coordinated in a monodentate way by three tridentate anions and two tetradentate ones. The coordination numbers of the outer Cs+ cations are equal to 10 for Cs(1), and 16 for Cs(2). The dioxocations AmO2 in both structures are linear and almost symmetric. Analysis of the obtained absorption spectra showed that the number and intensity of the absorption bands in them are dependent both on the equatorial ligand nature, and on the americium ion electronic configuration.
    No preview · Article · Jan 2014 · Radiochimica Acta
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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.
    No preview · Article · Nov 2013 · Radiochimica Acta
  • 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.
    No preview · Article · Apr 2013 · Russian Journal of Coordination Chemistry
  • A. V. Gogolev · M. S. Grigoriev · N. A. Budantseva · A. M. Fedosseev
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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.
    No preview · Article · Mar 2013 · Russian Journal of Coordination Chemistry
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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.
    Full-text · Article · Jul 2012 · Fibre Chemistry
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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.
    No preview · Article · Apr 2012 · Radiochemistry
  • A. M. Fedoseev · N. A. Budantseva · A. A. Bessonov · V. P. Shilov
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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.
    No preview · Article · Apr 2012 · Radiochemistry
  • 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.
    No preview · Article · Jan 2012 · Russian Journal of Coordination Chemistry
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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.
    No preview · Article · Dec 2011 · Radiochemistry
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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.
    No preview · Article · Nov 2011 · Inorganic Chemistry
  • 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.
    No preview · Article · Oct 2011 · Radiochemistry
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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.
    No preview · Article · Sep 2011 · Russian Journal of Coordination Chemistry

  • No preview · Article · Jun 2011
  • 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.
    No preview · Article · Jun 2011 · Russian Journal of Coordination Chemistry

Publication Stats

529 Citations
83.18 Total Impact Points

Institutions

  • 2007-2015
    • The A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences
      Moskva, Moscow, Russia
  • 2005-2012
    • A. N. Frumkin Institute of Physical Chemistry and Electrochemistry
      Moskva, Moscow, Russia
  • 1998-2012
    • Russian Academy of Sciences
      • • A.N. Frumkin Institute of Physical chemistry and Electrochemistry
      • • Institute of Chemistry
      Moskva, Moscow, Russia
  • 2000
    • Karpov Institute of Physical Chemistry
      Moskva, Moscow, Russia