Ukrainian Chemistry Journal

Contents of Volume 81 №9 (2015)

THE OLDEST CHEMICAL EDITION OF THE COUNTRY "UKRAINSKII KHIMICHESKII ZHURNAL" IS 90 YEARS OF AGE

Inorganic and Physical Chemistry

VOLKOV S.V., SUBBOTIN V.V., DEMCHENKO P.Yu., YANKO O.G., KHARKOVA L.B., GLADYSHEVSKII R.Ye.
Synthesis and structure of the tetranuclear cluster rhenium selenosulfidobromide Re4Se4S4Br16
  • Summary: The rhenium selenosulfidobromide Re4Se4S4Br16 was obtained by a reaction of Re2O7 with a solution of Se in S2Br2 at 200 oС. Its crystal structure, determined by X-ray powder diffraction, belongs to the ReTeSCl4 structure type: Z=8, space group I–4-g7, lattice parameters a =10.9763(5), c =13.2450(7) Å , reliability factors RI =6.13, Rp =2.41, Rwp =3.21 %. As well as known isostructural analogs of the general formula Re4Chal8Hal16 (Chal – S, Se, Te; Hal – Cl, Br), the Re4Se4S4Br16 complex is an isolated molecular tetranuclear cluster Re4(m3-S) 4(SeBr2)4Br8, which contains [Re4(m3-S)4] cubane-like core formed from a nearly regular Re4 tetrahedron with single Re–Re bonds of 2.651—2.726 Å and with each triangular face capped symmetrically by a bridging m3-S-ligand. Each Re atom is further ligated by two terminal Br– ligands and one terminal neutral SeBr2 ligand. Density functional theory calculations show that the compound is a semiconductor with a band-gap of 1.47 eV, and the effective atomic charges are Re+1.2Se+0.5S–0.3(Br–0.35)4.
  • Keywords: selenosulfidobromide of rhenium, tetranuclear cluster, liquid chalcohalide medium, semiconductor.
  • pp.: 7 - 11

TRUNOVA Ye.K., BEREZHNYTSKAYA A.S., IVAKHA N.B., ROGOVTSOV A.A., SAVCHENKO I.A.
Monomeric and polymeric complexes of erbium (III) with β-dicarbonyl ligands
  • Summary: The new coordination compounds of Er(III) with unsaturated β-dicarbonyl ligands were synthesized. The radical polymerization of metal complexes was carried out and its kinetics was studied by dilatometric method. The composition and structure of monomeric and polymeric compounds were determined by the methods of elemental analysis, IR and electronic spectroscopy, thermogravimetry. It has been shown that in monomeric complexes ion erbium (III) coordinates 3 molecules of β-dicarbonyl ligands, and coordination sphere of the central atom is supplemented with two water molecules. The parameters of covalency of the Er–O were calculated. The method of dynamic light scattering in chloroform solution defined distribution of particle radius and the nanoscale of metal complexes and their polymers was defined. By electron microscopy the uniform distribution of the metal in the polymer matrix was determined.
  • Keywords: complexes, erbium, β-diketones, allil acetoacetate, metallopolymers, nanoparticles.
  • pp.: 12 - 18

DENISENKO I.N., ORANSKY D.A., VARZATSKII O.A.
First example of palladium catalysis of copper-mediated reactions hetarylhalides with ethyl bromodifluoroacetate
  • Summary: First realized copper-palladium promoted reaction of difluoromethyl- karbethoxylation of arylhalohenides. It is shown that the use of palladium catalysis can significantly improve the yield of the main reaction and reduce the contribution of adverse reactions in comparison with the previously described copperpromoted reactions. Proton NMR spectroscopy evaluated the composition, structure and spectral properties of the obtained compounds.
  • Keywords: difluoromethyl-carboethoxylation reaction, palladium catalysis, copper-promoted reactions, clathrohelates, Ullmann reaction.
  • pp.: 19 - 24

KOLOMIYETS Ye.A, BELYAKOV V.N., PALCHIK A.V., ANDRUSISHINA I.N.
Sorption of anions of arsenic (V) by organic-inorganic composite materials based anion exchanger Dowex SBR-P, containing oxides of zirconium (IV) and iron (III)
  • Summary: Composite organic-inorganic ion-exchange materials including organic anion exchanger Dowex SBR-P and zirconium (IV) and iron (III) compounds were synthesized and their sorption properties in relation to anions of arsenic (V) were studied. We investigated the effect of the concentration of arsenic in the initial solution and the effect of acidity on the sorption capacity of the sorbents. It is shown that in the neutral and alkaline media source anion exchange resin SBR-P is ineffective. Introduction of the hydrated oxides of zirconium (IV) and iron (III) increases the effective range of action of sorbents to alkaline media and significantly improves the selectivity of the sorption of arsenic (V) from solutions containing a large amount of chloride ions.
  • Keywords: organo-inorganic adsorbents, ferrum oxide, zirconium oxide, arsenic anions, selectivity.
  • pp.: 25 - 29

MESHKOVA S.B., NOVIKOVA N.S., KONDRAT’EVA R.V., DOGA P.G., NEDOSTUP V.I.
Luminescence of complex compounds of Tb3+ ions with diesters of aliphatic acids
  • Summary: Received data were showing expediency of spacered reagents synthesis for observation intensive luminescence as Tb3+ ion, as other lanthanides. It was established that the spacer length, connected coordination centers, has an important role.
  • Keywords: spacered ligands, terbium complexes, luminescence.
  • pp.: 30 - 35

MARTSINKO Ye.E.
Synthesis, structure and properties onium bis(xylarato)germanates
  • Summary: The optimal conditions for the isolation onium bis(xylarato)germanates with organic exoligands (L — nicotinic acid, nicotinamide, diphenylguanidine, 2-oxo-1-pyrrolidinylacetamide, diantipyrylmethane) have been determined and synthesized for the first time. The resulting coordination compounds were characterized by methods of elementary and X-Ray powder diffraction analysis, thermogravimetry, IR-specroscopy. The molecular formulas synthesized compounds (НL)2[Ge(H2Хylar)2]×nН2О (H5Хylar—xylaric acid) and scheme of bis(xylarato)germanates anion structure have been proposed.
  • Keywords: germanium dioxide, xylaric acid, onium compounds, complex anion.
  • pp.: 36 - 40

ElectroChemistry

MILOVANOVA O.I., MALYOVANYI S.M., PANOV E.V., GLUSHCHAK T.S.
Properties of nonstationary electroconductivity of SnO2 films at the reduction gases adsorption
  • Summary: The change mechanism of electroconductivity G of films based on SnO2/M (M = Pd, Pt, Pd+MoO3, Co3O4) nanocrystals, synthesized in nitrate melt has been studied. The G behavior pattern under interaction of SnO2/M with ethanol, butanol, acetone vapor at 200 °С can be explained within the framework of simple model of SnO2 film: film is formed of SnO2/M grains and intergranular region (mainly dopant M), primarily one type of SnO2 active sites take part in gas reaction, G behavior is formed by intergranular region as the gas reaction zone.
  • Keywords: SnO2, thick film, gas sensor.
  • pp.: 41 - 45

GUSEYNOV R.M., MAHMUDOV H.M., RADZHABOV R.A., BAHMUDKADIEVA Z.N., ZAYNUTDINOVA Z.A.
Вlocked electrode—solid electrolyte interface in chronoampero- and chronopotentiometric charging modes
  • Summary: The operational impedance technique in two models (chronoamperometric and chronopotentiometric was used to study the kinetics of the charging process of the blocked (inert) electrode—solid electrolite interface in the case of slow diffusion and adsorption–desorption of two different sort electrochemical active particles. As equivalent electric circuit the Jacobsen–West diffusion model (which correct for relatively “large” times or “small” as frequencies) is applied.
  • Keywords: solid electrolyte, blocked electrode, operational impedance, double electric layer, equivalent electric circuit.
  • pp.: 46 - 51

Chemistry of High-Molecular Compounds

KARABANOVA L.V., GOMZA Yu.P., BONDARUK O.N., NESIN S.D., VORONIN Ye.Ph., NOSACH L.V.
The nanocomposites based on polyurethane-poly(2-hydroxyethyl methacrylate) matrix and nanofiller densyl: thermodynamics of interactions and features of microstructure
  • Summary: The thermodynamic parameters of interaction between polymer matrix components and nanofiller densil during process of nanocomposites formation are determined. The structure of the created nanocomposites is investigated by SAXS. The dependence of the nanocomposite’s characteristics from the content of polymer matrix and concentration of nanofiller find out. It is shown that the nanocomposites based on polymer matrix contained 17% PHEMA characterized by thermodynamic stability and high adhesion of polymer components to the nanofiller densyl. This polymer matrix characterized by the beginning of the microphase separation between the polymer constituents. This allow to get the nanocomposites with high physico-mechanical properties due to homogeneous densil nanoparticles distribution.
  • Keywords: nanocomposite, polyurethane, poly(2-hydroxyethyl metacrylate), structure, thermodynamic of interactions, physico-mechanical properties.
  • pp.: 52 - 59

ALEKSEEVA T.T., YAROVAYA N.V., GORBATENKO A.N.
Effect of Ti-containing copolymer on thermal and optical properties of organic-inorganic interpenetrating polymer networks
  • Summary: The thermophysic and optical properties of organic-inorganic copolymers (OIC) on the basis of 2-hydroxyethylmethacrylate (HEMA) and titanium tetraisopropoxide as well as organic-inorganic interpenetrating polymer networks (OI IPN) on the basis of polyurethane (PU) network and OIC with varying (–TiO2–) fragments in the polymeric chain of polyhydroxyethylmethacrylate (PHEMA) were studied. It was established that introduction of a Ti-component into the composition of OI IPN improves thermal stability, mechanical durability on a break in the with the content of the 2.0—3.5%wt of (–TiO2–) fragments.With the increase of (–TiO2–) fragments content the ability of optical absorbance of polymeric Ti-containing materials at induced UV-radiation rises.
  • Keywords: interpenetrating polymer networks, polyhydroxyethylmethacrylate, polyurethane, titanium isopropoxide, thermal stability, mechanical durability, optical absorbance.
  • pp.: 60 - 66

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