Stratification in a ternary liquid system [Th(NO3)4(TBP)2]-[UO2(NO3)2(TBP)2]-Exide 100 solvent at various temperatures

Phase diagram of a ternary liquid system [Th(NO₃)₄(TBP)₂]-[UO₂(NO₃)₂(TBP)₂]-Exide 100 solvent was studied at 298.15–333.15 K. Original Russian Text ? A.K. Pyartman, V.A. Keskinov, V.V. Lishchuk, Ya.A. Reshetko, V.E. Skobochkin, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 8, pp. 1243–1245.     

Structure and magnetic and electric properties of bismuth niobates doped with d elements: IV. Magnetic behavior of chromium-containing solid solutions with the structure of bismuth niobate, Bi5Nb3O15

The magnetic susceptibility and electrophysical properties of chromium-containing Bi₅Nb_3−3x · Cr_3x O_15−δ solid solutions with the perovskite-like structure were studied. Parameters of exchange interactions in the dimeric clusters of chromium atoms and also the distribution of chromium monomers and dimers in the solid solutions were calculated. Original Russian Text ? N.A. Zhuk, I.V. Piir, A.L. Pimenov, N.V. Chezhina, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 6, pp. 898–904. For communication III, see [1].     

Synthesis, structure, and properties of [Re2(HPO4)2(H2PO4)2(H2O)2] · 4H2O

The complex [Re₂(HPO₄)₂(H₂PO₄)₂(H₂O)₂] · 4H₂O (I) was synthesized and investigated by conductometric, potentiometric, electronic and vibration spectroscopic methods. Thermal behavior of the title compound was studied and its molecular structure was determined from X-ray diffraction data. In the dimeric neutral complex, the bridging pairs of the hydrophosphate and dihydrophosphate groups close four five-membered Re-O-P-O-Re chelate rings. The O atom of water molecule occupies the axial position in the metal coordination polyhedron. The Re-Re distance 2.2168(8) ? corresponds to quadruple bond. Original Russian Text ? A.V. Shtemenko, V.G. Stolyarenko, K.V. Domasevich, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 2, pp. 83–88.     

Double complex salts [Pt(NH3)5Cl][M(C2O4)3] · n H2O (M = Fe, Co, Cr): Synthesis and study

Double complexes [Pt(NH₃)₅Cl][Fe(C₂O₄)₃] · 4H₂O, [Pt(NH₃)₅Cl][Co(C₂O₄)₃] · 2H₂O, and [Pt(NH₃)₅Cl][Cr(C₂O₄)₃] · 4H₂O were synthesized and studied by single-crystal X-ray diffraction, X-ray phase analysis, differential thermal analysis, elemental analysis, and IR spectroscopy. The crystal structures of the compounds were examined from the viewpoint of the close packing of coordination polyhedra. The thermal properties of the synthesized complexes and K₃[M(C₂O₄)₃] salts (M = Fe, Co, Cr) were compared. A procedure for the synthesis of the FePt, CoPt, and CrPt intermetallic compounds through the thermolysis of the obtained complexes was developed. Original Russian Text ? K.V. Yusenko, D.B. Vasil’chenko, A.V. Zadesenets, I.A. Baidina, Yu.V. Shubin, S.V. Korenev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1589–1593.     

Preparation of nanopowdered M1? x R x F2+ x (M = Ca, Sr, Ba; R = Ce, Nd, Er, Yb) Solid Solutions

The synthesis procedure has been worked out, and nanopowders of fluoride solid solutions (ss) Ca_1−x R _x F_2+x (R = Er, Yb), Sr_1−x Nd _x F_2+x , and Ba_1−x Ce _x F_2+x have been manufactured by coprecipitation from aqueous solutions. The powders consist of rounded particles with sizes from 50 to 150 nm. The particles with sizes of about 150 nm are aggregates of adhered nanoparticles. The nanoparticles are highly reactive and sinter at low temperatures (T < 0.35T _m). Original Russian Text ? S.V. Kuznetsov, I.V. Yarotskaya, P.P. Fedorov, V.V. Voronov, S.V. Lavrishchev, T.T. Basiev, V.V. Osiko, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 3, pp. 364–369.     

Complex salts (DienH3)[IrCl6](NO3), (DienH3)[PtCl6](NO3), and (DienH3)[IrCl6]0.5[PtCl6]0.5(NO3): Synthesis, structure, and thermal properties

The complex salts ((DienH₃)[IrCl₆](NO₃) (I), (DienH₃)[PtCl₆](NO₃) (II), and (DienH₃)[IrCl₆]_0.5[PtCl₆]_0.5(NO₃) (III) (where Dien is NH₂(CH₂)₂NH(CH₂)₂NH₂) were synthesized and characterized by elemental, X-ray diffraction, and thermal analyses and by electronic and IR spectroscopies. Solid solution of the composition Ir_0.35Pt_0.65 was obtained by decomposition of compound III in the atmosphere of hydrogen. Original Russian Text ? E.V. Makotchenko, I.A. Baidina, P.E. Plusnin, L.A. Sheludyakova, Yu.V. Shubin, S.V. Korenev, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 47–54.     

Cu(II) complexes with 4,6-bis(3,5-dimethyl-1 H -pyrazole-1-yl)pyrimidine, 4-(3,5-dimethyl-1 H -pyrazole-1-yl)-6-(3,5-diphenyl-1 H -pyrazole-1-yl)pyrimidine: Synthesis and catalytic activity in ethylene polymerization reaction

The Cu(II) complexes with 4,6-bis(3,5-dimethyl-1H-pyrazole-1-yl)pyrimidine (L¹) and 4-(3,5-dimethyl-1H-pyrazole-1-yl)-6-(3,5-diphenyl-1H-pyrazole-1-yl)pyrimidine (L²) of the composition Cu₂L¹Br₄ and Cu₂L²A₄ (A = Cl, Br), respectively, were synthesized and studied by IR and magnetochemical methods. The molecular structure of the complexes is likely to be binuclear. In the presence of cocatalysts methylaluminoxane and triisobutylaluminium, the title complexes exhibit catalytic activity in the ethylene polymerization reaction. Original Russian Text ? M.B. Bushuev, V.P. Krivopalov, N.V. Semikolenova, Yu.G. Shvedenkov, L.A. Sheludyakova, G.G. Moskalenko, L.G. Lavrenova, V. A. Zakharov, S.V. Larionov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 8, pp. 612–617.     

State of atoms of the transition group elements in dilute solid solutions based on LiMO2 (M = Sc, Ga, Al): II. Magnetic characteristics of nickel atoms in LiNi x Sc1 ? x O2 solid solutions

The state of nickel atoms in LiNi _x Sc_{1 − x} O₂ solid solutions was studied. The anomalous magnetic characteristics can be accounted for only by the presence of dilution-resistant clusters containing Ni(III) in two states: high- and low-spin. Original Russian Text ? A.A. Selyutin, N.P. Bobrysheva, N.V. Chezhina, A.V. Shchukarev, A.O. Kozin, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 10, pp. 1608–1612. For communication I, see [1].     

4-functionally substituted 3-heterylpyrazoles: XVIII. Intramolecular cyclization of N -[3-(2-Chlorophenyl)-4-pyrazolyl]methylamine and its N-alkyl derivatives into 4,5-dihydro-2 H -pyrazolo[4,3- c ]quinolines

N-[3-(2-Chlorophenyl)-4-pyrazolyl]methylamine and its N-alkyl-derivatives at heating in DMF in the presence of K₂CO₃ undergo an intramolecular cyclocondensation yielding 4,5-dihydro-2H-pyrazolo[ 4,3-c]quinolines. Original Russian Text ? M.K. Bratenko, O.I. Panimarchuk, V.A. Chornous, M.V. Vovk, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 8, pp. 1213–1216. For Communication XVII see [1].     

Crystallization and dielectric and optical properties of borate glasses (1 ? x)Na2B4O7 + xNb2O5

The crystallization and dielectric and optical properties of glasses (1 − x)Na₂B₄O₇ + xNb₂O₅, where x = 0.15–0.35, have been studied. The formation of structural entities based on NbO₆ octahedra in the glass has been detected by Raman spectroscopy. In the thermally poled glass, a layer with nonlinear optical properties is formed under the anode surface. The nonlinear optical properties of the poled sample have been studied by the second harmonic generation method using laser radiation. The nonlinear optical coefficient d ₃₃ for the poled glass with the maximal content of niobia is 0.1 pm/V. Original Russian Text ? A.P. Malakho, S.Yu. Stefanovich, V.A. Morozov, B.I. Lazoryak, E. Fargin, V. Rodriguez, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 3, pp. 349–356.     

Synthesis, properties, and thermal decomposition products of [Ru(NH3)5Cl][PtCl6] and [Ru(NH3)5Cl]2[PtCl6]Cl2

The double complex salts [Ru(NH₃)₅Cl][PtCl₆] (I) and [Ru(NH₃)₅Cl]₂[PtCl₆]Cl₂ (II) were synthesized and studied by X-ray diffraction. They were found to be isostructural to the previously synthesized [Rh(NH₃)₅Cl][OsCl₆] and [Ir(NH₃)₅Cl]₂[PtCl₆]Cl₂. The thermolysis of the complexes in the atmosphere of hydrogen and helium was studied by the powder X-ray diffraction analysis. The product of the salt I thermolysis is a single-phase solid solution Ru_0.5Pt_0.5 (a = 3.857(3) ?), the thermolysis of salt II results in a double-phase metallic powder. Original Russian Text ? S.A. Martynova, K.V. Yusenko, I.V. Korol’kov, S.A. Gromilov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 7, pp. 541–545.     

Densities and Volumetric Properties of Binary Mixtures of Formamide with 1-Butanol, 2-Butanol, 1,3-Butanediol and 1,4-Butanediol at Temperatures between 293.15 and 318.15 K

The densities of binary mixtures of formamide (FA) with 1-butanol, 2-butanol, 1,3-butanediol, and 1,4-butanediol, including those of the pure liquids, over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, V _m ^E, partial molar volumes, and , at infinite dilution, and excess partial molar volumes, and , at infinite dilution were calculated. The variation of these parameters with composition and temperature of the mixtures are discussed in terms of molecular interactions in these mixtures. The partial molar expansivities, and , at infinite dilution and excess partial molar expansivities, and , at infinite dilution were also calculated. The V _m ^E values were found to be positive for all the mixtures at each temperature studied, except for FA + 1-butanol which exhibits a sigmoid trend wherein V _m ^E values change sign from positive to negative as the concentration of FA in the mixture is increased. The V _m ^E values for these mixtures follow the order: 1-butanol < 2-butanol < 1,3-butanediol < 1,4-butanediol. It is observed that the V _m ^E values depend upon the number and position of hydroxyl groups in these alkanol molecules.     

Magnetic and thermodynamic properties of Heisenberg chains and n -nuclear cyclic clusters: S i = 5/2, S i = 3, and S i = 7/2 systems

Based on the previously developed method considering spin and point symmetry, numerical calculations of spin-level spectra have been performed for n-nuclear cyclic clusters with S _i = 5/2 (n ≤ 9), S _i = 3 (n ≤ 8), and S _i = 7/2 (n ≤ 8). The theoretical curves of the magnetic susceptibility, the magnetic contribution to the heat capacity, and the internal energy as a function of temperature have been obtained. The theoretical curves of the magnetic susceptibility and magnetic contribution to the heat capacity have been extrapolated to n → ∞ with a controlled accuracy. These curves are compared to available data. Original Russian Text ? Yu.V. Rakitin, O.R. Starodub, V.M. Rakitina, V.T. Kalinnikov, V.M. Novotortsev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 3, pp. 448–455.     

Cluster compounds [Ca(DMF)6][Mo6Cl14] and [{Ca(OPPh3)4}{Mo6Cl14}]∞: Synthesis, crystal structure, and properties

The [Ca(DMF)₆][Mo₆Cl₁₄] complex (I) was synthesized by reacting octahedral cluster Mo complex (H₃O)₂Mo₆Cl₁₄·6H₂O with the Ca²⁺ cation in DMF. Analogous reaction carried out in the presence of triphenylphosphine oxide Ph₃PO in acetonitrile resulted in [{Ca(OPPh₃)₄}{Mo₆Cl₁₄}] (II). According to X-ray diffraction data, complex I has ionic structure, while the structure of complex II consists of infinite linear chains of the cluster anionic complexes {Mo₆Cl₁₄}²⁻ bonded to the cationic Ca complexes {Ca(OPPH₃)₄}²⁺. Both complexes exhibit intensive luminescence in red and near-IR regions of the spectrum. Original Russian Text ? Zh.S. Kozhomuratova, Yu.V. Mironov, M.A. Shestopalov, Ya.M. Gaifulin, N.V. Kurat’eva, E.M. Uskov, V.E. Fedorov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 3–8.     

Thermodynamic calculations of phase equilibria in the neodymium-barium-copper-oxygen system: A model of the Nd1 + x Ba2 ? x Cu3O6 + z phase

A thermodynamic model of the Nd_{1 + x} Ba_{2 − x} Cu₃O_{6 + z} phase is suggested. The model allows the properties and boundaries of the regions of various phase polymorphs to be described within the framework of a unified solid solution. Analytic equations for the Gibbs energy and chemical potentials of the components and the other thermodynamic functions of Nd_{1 + x} Ba_{2 − x} Cu₃O_{6 + z} were obtained. Original Russian Text ? V.A. Lysenko, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 8, pp. 1358–1363.     

Composite films of polyaniline and molybdenum oxide formed by electrocodeposition in aqueous media

Composite films of polyaniline (PANI) and molybdenum oxide (MoO_x) were afforded through a convenient route of electrocodeposition from aniline and (NH₄)₆Mo₇O₂₄. The composite films showed characteristic redox behaviors of PANI and MoO_x, respectively, on the cyclic voltammograms. Chlorate and bromate were catalytically electroreduced with an enlarged current on the composite film at a potential ca. 0.2 V more positive than that on MoO_x. The potential window for the composite film to display pseudocapacitive properties in 1.0 mol·dm⁻³ NaNO₃ was −0.6 ∼ 0.6 V vs SCE. The cathodic potential limit shifted at least 0.4 V negatively from that of polyaniline (PANI)-based materials reported so far. The specific capacitance was 363.6 F·g⁻¹ when the composite film was charged–discharged at 1.5 mA·cm⁻², about two times of that of the similarly prepared PANI. The composite film was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Molybdenum existed in a mixed state of +5 and +6 in the composite film based on XRD and XPS investigations. Figure PANI and (MoO_x) were electrocodeposited in aqueous solutions from aniline and (NH₄)₆Mo₇O₂₄. The composite film obtained displayed catalytic activities toward the electroreduction of oxoanions. The pseudocapacitance of the composite film is nearly two times of that of PANI with the potential window extended negatively up to −0.6 V vs SCE     

Ab initio calculations of group IVA tetrachloride complexes: IV. Dynamics of the formation of the complex of SiCl<Subscript>4</Subscript> with trimethylamine

Quantum-chemical calculations of the system SiCl₄←N(CH₃)₃ were fulfilled by the RHF/6-31G(d) and B3LYP/6-311G(d) methods with full geometry optimization at varied Si←N distances. The experimental electronic and steric structure of the complex were fit not on full geometry optimization but on the geometry optimization with the Si←N distance fixed at the experimental estimate. The calculations showed that the components polarize each other as come closer together. Furthermore, the electron density is transferred from the H atoms of the donor onto the Cl atoms of the acceptor. The C, N, and Si atoms serve only as electron density conductors. Original Russian Text V.P. Feshin, E.V. Feshina, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 5, pp. 786–791. For communication XX, see [1].     

Phase formation in Fe0-H2O-O2 system in the presence of iron cations: 2. Fe0-H2O-O2-Fe2(SO4)3 system

Formation mechanisms of ultradispersed (nanosized) iron-oxygen particles in a Fe⁰-H₂O-O₂ system in the presence of trivalent iron cations are investigated. It is shown that, depending on the solution concentration and pH and the presence or absence of an oxidant on the surface of iron, nanosized nuclei, mainly ferrihydrite, are formed in the surface layer and in the solution. Further growth of these nuclei occurs via several mechanisms to yield ultradispersed phases of iron oxides and monohydrates with different crystalline modifications. Original Russian Text ? V.A. Prokopenko, E.N. Lavrinenko, S.V. Mamunya, 2007, published in Kolloidnyi Zhurnal, 2007, Vol. 69, No. 1, pp. 88–95.     

Reactions of heterocumulenes with organometallic reagents: XIII. Quantum-chemical study on the mechanisms of syn -( Z )/ anti -( E )-isomerization of methyl 2-methoxy- N -methylbuta-2,3-dienimidothioate

Mechanisms of syn-(Z)/anti-(E) isomerization of methyl 2-methoxy-N-methylbuta-2,3-dienimidothioate, including rotational, inversion, promoted by N-protonation, and nucleophile-catalyzed, were studied by quantum-chemical methods, and the corresponding thermodynamic and kinetic parameters were calculated. The most probable mechanisms of isomerization of buta-2,3-dienimidothioates were found to be inversion (E _a = 74.4 kJ/mol) and nucleophile-catalyzed (E _a = 61.6 kJ/mol). Original Russian Text ? V.A. Shagun, N.A. Nedolya, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 11, pp. 1591–1600. For communication XII, see [1].     

Butadiene–isoprene copolymerization with V(acac)3‐MAO. Crystalline and amorphous trans‐1,4 copolymers

Butadiene‐isoprene copolymerization with the system V(acac)₃‐MAO was examined. Crystalline or amorphous copolymers were obtained depending on isoprene content. Both butadiene and isoprene units exhibit a trans‐1,4 structure and are statistically distributed along the polymer chain. Polymer microstructure, comonomer composition, and distribution along the polymer chain were determined by ¹³C and ¹H NMR analysis. The thermal and X‐ray behaviors of the copolymers were also investigated and compared with results from solid‐state ¹³C NMR experiments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4635–4646, 2007