Formation of heteropolynuclear cobalt(II) and nickel(II) complexonates with EDTA and 2-aminopropanoic acid

Coordination equilibria in the Co(II)–Ni(II)–2-aminopropanoic acid (HAla)–EDTA system have been studied spectrophotometrically at different molar ratios of the reagents in a wide pH range. It has been found that, when metal ions are in excess with respect to EDTA at pH 5–9, polyheteronuclear complexonates [(CoAla)Edta(NiAla)]^2–, [(CoAla₂)Edta(NiAla₂)]^4–, [(NiAla₂)Edta(CoAla₂)₂]^4–, [(CoAla₂)Edta(NiAla₂)₂]^4–, and [(NiAla₂)₂Edta(CoAla₂)₂]^4– form in a solution. The equilibrium constants of formation of these complexes and their overall stability constants have been calculated. Possible structures of the polynuclear complexonates are discussed.     

Synthesis and properties of double copper(I)–nickel(II) sulfite

Pourbaix diagrams of Cu–H₂SO4–H₂O and Ni–H₂SO₄–H₂O systems have been refined, and stability regions of the sulfite phases have been determined. State diagrams of double copper(I)–copper(II) and copper(I)–nickel(II) sulfites have been constructed. Double copper(I)–nickel(II) sulfite has been isolated from aqueous solutions saturated with sulfur dioxide. The solutions at different ratios of the metals have been studied by spectrophotometry; the isolated double sulfite has been studied by X-ray diffraction, IR spectroscopy, dispersion analysis, and thermal analysis. Fundamentals of thermodynamic prognostication of the Cu₂SO₃·MSO₃ double sulfites synthesis have been elaborated.     

Preparation of double pyrophosphates in aqueous systems chromium(III) salt−sodium pyrophosphate

The specifics of preparation of chromium double pyrophosphates in systems Cr(NO₃)₃–Na₄P₂O₇–H₂O, CrCl₃–Na₄P₂O₇–C₂O, and KCr(SO₄)₂–Na₄P₂O₇–H₂O are discussed. Changes in pH of the mentioned systems have been studied depending of the component ratio. The effects of the deposition duration and sodium pyrophosphate concentration on pH have been studied for system Cr(NO₃)₃–Na₄P₂O₇–H₂O. Phase composition has been determined for compounds prepared in systems Cr(NO₃)₃–Na₄P₂O₇–H₂O and KCr(SO₄)₂–Na₄P₂O₇–H₂O. It has been found that the acid residue anions do not substantially affect the formation of a continuous series of compounds consisting of hydroxy and hydro combinations of chromium ions and pyrophosphate ion, whereas cations can have an effect. System KCr(SO₄)₂–Na₄P₂O₇–C₂O is less sensitive to reaction conditions than systems in which normal salts Cr(NO₃)₃ and CrCl₃ act as a source of Cr³⁺ cation. A product stable over time can be prepared in system KCr(SO₄)₂–Na₄P₂O₇–C₂O; after heat treatment at 900°C, it is a mixture of KCrP₂O₇ and a-CrPO₄ phases.     

Ethoxytelluration of Terminal Alkenes with Tellurium Tetrahalides

Efficient methods for the preparation of trichloro- and tribromo(2-ethoxyalkyl)-λ⁴-tellanes in 80 to 100% yield have been developed on the basis of ethoxytelluration of hex-1-ene, hept-1-ene, and oct-1-ene with tellurium tetrahalides. Tribromo(2-ethoxyalkyl)-λ⁴-tellanes have been reduced to 1,2-bis(2-ethoxyalkyl)ditellanes in 92–95% yield with the system NaBH₄–H₂O–THF.     

Effect of Synthesis Method on the Phase Composition and Ion-Exchange Properties of Titanium Phosphate

Relationships between synthesis conditions, phase composition, and ion-exchange properties have been analyzed on the basis of results of physicochemical study for reaction products in the (NH₄)₂TiO(SO₄)₂–H₃PO₄–H₂O system. Mechanisms have been suggested for the formation of final titanium phosphate phase in different synthesis methods.     

Phase equilibria in the oxide system Nd2O3–K2O–P2O5

A phase equilibria diagram of the partial system NdPO₄–K₃PO₄–KPO₃ has been developed as part of the research aimed at determining the phase equilibrium relationships in the oxide system Nd₂O₃–K₂O–P₂O₅. The investigations were conducted using thermoanalytical techniques, X-ray powder diffraction analysis and reflected-light microscopy. Three isopleths existing between: K₃Nd(PO₄)₂–K₄P₂O₇, NdPO₄–K₅P₃O₁₀ and NdPO₄–K₄P₂O₇ have been identified in the partial NdPO₄–K₃PO₄–KPO₃ system. Previously unknown potassium-neodymium phosphate “K₄Nd₂P₄O₁₅” has been discovered in the latter isopleth section. This phosphate exists in the solid phase up to a temperature of 890 °C at which it decomposes into the parent phosphates NdPO₄ and K₄P₂O₇. Four invariant points: two quasi-ternary eutectics, E₁ (1057 °C) and E₂ (580 °C) and two quasi-ternary peritectics, P₁ (1078 °C) and P₂ (610 °C), occur in the NdPO₄–K₃PO₄–KPO₃ region.     

Hierarchical Fe3O4@TiO2 Yolk–Shell Microspheres with Enhanced Microwave‐Absorption Properties

A facile and efficient strategy for the synthesis of hierarchical yolk–shell microspheres with magnetic Fe₃O₄ cores and dielectric TiO₂ shells has been developed. Various Fe₃O₄@TiO₂ yolk–shell microspheres with different core sizes, interstitial void volumes, and shell thicknesses have been successfully synthesized by controlling the synthetic parameters. Moreover, the microwave absorption properties of these yolk–shell microspheres, such as the complex permittivity and permeability, were investigated. The electromagnetic data demonstrate that the as‐synthesized Fe₃O₄@TiO₂ yolk–shell microspheres exhibit significantly enhanced microwave absorption properties compared with pure Fe₃O₄ and our previously reported Fe₃O₄@TiO₂ core–shell microspheres, which may result from the unique yolk–shell structure with a large surface area and high porosity, as well as synergistic effects between the functional Fe₃O₄ cores and TiO₂ shells.     

Structural diversity of a series of urea-based coordination complexes: from water tapes,water-sulfate chains,to supramolecular structures

[Hg₂(L₁)₂I₄] (1), [Cd₂(L₁)₂I₄] (2), {[Cd(L₁)₂(SO₄)(H₂O)]·4H₂O}_n (3), {[Zn₂(L₂)₂(Cl)₄]·0.5H₂O} (4), {[Cu₂(L₂)₂(SO₄)₂(H₂O)₄]·2.5H₂O} (5), and {[Cd(L₂)₂(SO₄)(H₂O)]·3H₂O}_n (6), based on N–(3–picolyl)–N′–(3–pyridyl)urea (L₁) or N–(4–picolyl)–N′–(3–pyridyl)urea (L₂), have been synthesized and characterized by elemental analyses, IR spectra, single-crystal and powder X-ray diffraction, and thermogravimetric analyses. Complexes 1 and 2 are isomorphous and feature similar rectangular metal organic loops, which were further extended into 2-D supramolecular structures through hydrogen bonds. Complex 3 possesses a 2-D sql sheet, and the channels between the neighboring sheets are filled with lattice water molecules, which formed a 1-D water tape. Complex 4 also exhibits a rectangular metal organic loop and a 3-D supramolecular structure with the help of hydrogen bonding interactions. Complex 5 also possesses a metal organic loop, and the water molecules interacted with sulfates, constructing a 1-D water–sulfate tube. Complex 6 features a 1-D loop polymeric chain. Moreover, the solid state luminescences of 1–4 and 6 have been investigated.     

Thermodynamic properties of lanthanum molybdates

The enthalpy of solution of LаОНMoO₄ and Cs₂MoO₄ in aqueous HCl at 298 К has been determined by solution calorimetry, and the standard enthalpy of formation of lanthanum hydroxomolybdate has been calculated. The enthalpies of solution of NaLa(MoO₄)₂ and Na₅Lа(MoO₄)₄ in molybdate melt at 973 K have been determined by high-temperature melt solution microcalorimetry, and the high-temperature enthalpies of the double molybdates in the 298–1000 K range have been measured by the mixing method. The standard enthalpies of formation of the double molybdates have been calculated using data available from the literature. The low-temperature heat capacity of NaLa(MoO₄)₂ in the 60–300 K range has been measured on an adiabatic vacuum calorimeter. The basic thermodynamic properties of NaLa(MoO₄)₂, Na₅Lа(MoO₄)₄, and LаОНMoO₄ have been calculated.     

Das System Ammoniumnitrat-Ammoniumdihydrogenphosphat-Harnstoffnitrat- Harnstoffphosphat-Wasser

The System Ammonium Nitrate–Monoammonium Phosphate–Urea Nitrate–Urea Phosphate–Water The 20 and 40°C isotherms of the quaternary system ammonium nitrate– monoammonium phosphate–urea nitrate–urea phosphate–water have been determined by an analytical method. NH₄H₂PO₄ and CO(NH₂)₂·HNO₃ form a stable ternary system at both temperatures.     

Solvothermal Synthesis,Crystal Structure and Properties of the First Organic‐templated Holmium Sulfate [C2N2H10]3[Ho2(SO4)6·2H2O]

The first organic amine‐templated holmium sulfate [C₂N₂H₁₀]₃[Ho₂(SO₄)₆·2H₂O] ( 1 ) has been synthesized solvothermally and has been structurally characterized by single‐crystal X‐ray diffraction studies, IR spectroscopic, thermogravimetric (TG) and inductivity coupled plasma (ICP) measurements. Crystal analyses of compound 1 showed a novel inorganic layer constructed from the zigzag and helical [–Ho–O–S–O–]_n chains, both of the chains are connected by μ‐2 SO₄^2– groups to form 10‐membered rings. The solvent plays an important role during the formation of 1 .     

The features of ignition of hydrogen–methane and hydrogen–isobutene mixtures with oxygen over Rh and Pd at low pressures

The flammability limits of stoichiometric mixtures (20–80% H₂ + 80–20% CH₄) + O₂ over Rh and Pd were determined in the pressure range 0–200 Torr and the temperature range 200–500 °C. It has been shown that the dark reaction in the mixture (80% H₂ + 20% C₄H₈)_stoich + O₂ leads to the formation of carbon nanotubes with a mean diameter of 10–100 nm.     

Monomer-isomerization polymerization. XVI. Monomer-isomerization polymerization of methylpentenes with Ziegler-Natta catalyst

The polymerizations of 4-methyl-1-pentene(4M1P), 4-methyl-2-pentene (4M2P), 2-methyl-2-pentene (2M2P), and 2-methyl-1-pentene (2M1P) with Ziegler-Natta catalyst have been investigated. Both 4M1P and 4M2P were found to polymerize with TiCl₃–(C₂H₅)Al catalyst to give high molecular weight poly(4M1P), while 2M2P and 2M1P did not give polymers with 4M1P units. However, when the polymerizations of 2M1P and 2M2P were carried out with ternary catalyst systems, TiCl₃–(C₂H₅)AlCl–(PPh₃)₂PdCl₂ and TiCl₃–(C₂H₅)AlCl–Ni(SCN)₂ polymers with 4M1P units were obtained in low yield. It was concluded that these four methylpentenes could polymerize with the monomer-isomerization polymerization mechanism to poly(4M1P). The results of the observed isomer distribution of methylpentenes recovered, and the rate of polymerization of four methylpentenes suggest that the isomerization from 2M1P to 4M1P with the above ternary catalyst systems might proceed via a direct one-step isomerization mechanism.     

Study of simultaneous solubility of salts in the ammonium nitrate–ammonium chloride–water system

Ternary eutectic of the NH₄NO₃–NH₄Cl–H₂O system at–23.6°С has been found using a set of theoretical and experimental methods. According to the data of visual-polythermal and differential thermal analyses data, crystallization surface of the system has been plotted at–23.6 to 100°С.     

Reduction of Disilane (tBu3Si)Br2Si‐SiBr2(SitBu3) in Presence of C2H4: A Mechanistic Approach

The reduction of R*–SiBr₂–SiBr₂–R* ( 2 ) with NaR* (R* = supersilyl = SitBu₃) in presence of C₂H₄ provides a white crystalline solid (η²‐C₂H₄)R*Si–SiR*(Br)(CH₂–CH₂–R*) ( 3 ) characterized by X‐ray diffraction analysis. Compound 3 is accompanied with an impurity of R*(Br)₂Si–Si(Br)(R*)(CH₂–CH₂–R*) ( 4 ). The formation of 3 and 4 runs complicated because of several reactive partners. However, reduction of 2 with sodium naphthalenide in presence of ethene runs straightforward with formation of a mixture of tetrahedrane R*₄Si₄ ( 1 ) and bis(silirane) R*(η²‐C₂H₄)Si–Si(η²‐C₂H₄)R* ( 5 ). The latter is formed by [1+2]‐cycloaddition reaction of intermediate disilyne R*Si≡SiR* with ethene. Compound 5 has been characterized by X‐ray structure determination. The ¹H NMR spectrum of the silacyclopropane ring protons shows AA′BB′ complex spectrum comprising of 2 sets each of 12 transitions.     

Special features of preparation of nanosized zirconium diboride powders of various dispersity

Products of the zirconium powder reaction with amorphous boron in a Na₂B₄O₇ ionic melt at 650–850°C and those of the ZrCl₄ reaction with NaBH₄ at 300–725°C have been studied by means of X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, thermogravimetry, and elemental analysis. At temperature ≥750°C, single-phase ZrB₂ with the particle size of 60–80 nm is formed in a Na₂B₄O₇ ionic melt, whereas the ZrB₂ powder obtained via the reaction of ZrCl₄ with NaBH₄ at temperature ≥575°C consists of particles differing in the shape, some of which are close to spherical with diameter of 10–35 nm.     

Activation of – N=CH – bond in a Schiff base by divalent nickel monitored by NMR evidence

The Schiff base, 2–salicylidene–4–aminophenyl benzimidazole in ethanol undergoes activation of –N=CH– bond by Ni²⁺ in the presence of ammonia or primary alkyl amine to produce nickel complexes of the formula Ni{o–C₆H₄(O)CH NR}₂ . n H₂O [R = H, Me; n = 0; R = Et, n = 0.5] and 4–aminophenyl benzimidazole. The products have been identified by elemental analysis, magnetic susceptibility measurements and IR, ESR, mass and extensive NMR spectral studies. The possible mechanism for the activation of –N=CH – bond has also been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

A Spectrophotometric Study of Fe(III) Chelates of Some Hydroxy Coumarin Derivatives

Chelates formation of Fe(III) with 7–hydroxy–4–methyl coumarin–6–carboxylic acid (HMCCH)₂ and 8–amino–7–hydroxy–4–methyl coumarin (AHMCH) have been studied. It has been observed that Fe(III) forms 1:2 (metal:ligand) chelates with HMCCH₂ and AHMCH. The stability constants of these chelates at different ionic strengths and the effect of temperature on the stability constants of these chelates have been studied. The thermodynamic parameters such as entropy change (ΔS), free energy of formation (ΔG) and enthalpy change (ΔH) have also been calculated. The effect of dielectric constant oh the stability constants of these chelates have been studied. Estimation of nanogram quantities of Fe(III) with these ligands and the effect of diverse ions have also been studied and the results have been compared with other methods used for estimation of Fe(III).     

Halogenid‐Ionen als Katalysator: Metallzentrierte C–C‐Bindungsknüpfung ausgehend von Acetontril

Halide Ions as Catalyst: Metalcentered C–C Bond Formation Proceeded from Acetonitril AlMe₃ reacts at 20 ?C in acetonitrile to the complex [Me₃Al(NCMe)] ( 1 ). By addition of cesium halides (X^– = F^–, Cl^–, Br^–) a trimerisation to the heterocycle [Me₂Al{HNC(Me)}₂C(CN)] ( 2 ) has been observed. The reaction might be carried out under catalytic conditions (1–2 mol% CsX). The gallium complex [Me₂Ga{HNC(Me)}₂ · C(CN)] ( 3 ), generated under similar reaction conditions, can be converted to the silylated compound [Me₂Ga{Me₃SiNC(Me)}₂C(CN)] ( 4 ) by successive treatment with two equivalents n‐butyllithium and Me₃SiCl. 3 reacts under hydrolysis conditions (1 M hydrochloric acid) to the iminium salt [{H₂NC(Me)}₂C(CN)]Cl ( 5 ). A mixture of H₂O, Ph₂PCl and 3 in THF/toluene leads in a unusual conversion to the diphospane derivative [Ph₂P–P(O)(Me₂GaCl)] ( 6 ). 1 , 2 , 4 , 5 and 6 have been characterized by NMR, IR and MS techniques. X‐ray structure analyses were performed with 1 , 2 , 4 and 6 · 0.5 toluene. According this 1 possesses an almost linear axis AlNCC [Al1–N1–C3: 179,5(2)?; N1–C3–C4: 179,7(4)?]. 2 is an AlN₂C₃ six‐membered heterocycle with two iminium fuctions. One N–H group is responsible for a intermolecular chain‐formation through hydrogen bridges to an adjacent nitrile group along the direction [010]. The basic structural motif of the heterocycle 3 has been maintained after silylation to 4 . In 6 · 0.5 toluene an unit Me₂GaCl, originated from 3 , is coordinated to the oxygen atom of the diphosphane oxide Ph₂P–P(O)Ph₂.     

The new experimental data and a new thermodynamic model based on group contribution for correlation liquid–liquid equilibria in aqueous two-phase systems of PEG and (K2HPO4 or Na2SO4)

The new experimental data of liquid–liquid equilibria for aqueous two-phase systems PEG–K₂HPO₄–water and PEG–Na₂SO₄–water are presented. The effects of pH and molecular weight of polyethylene glycol were investigated and the tie lines with binodal curves for both systems are shown. A new thermodynamic model based on group contribution has been proposed for studying the phase behavior of aqueous two-phase polymer–salt systems. The assumptions of NRTL-NRF model and the activity coefficient equation of UNIQUAC-NRF model have been used for the groups. In this new model, UNIFAC-NRF, the nonrandom state of groups were selected as a reference state. The binary interaction parameters were adjusted using the data of binary salt–water systems and the ternary systems were correlated with only six binary adjustable parameters. The Debye–Huckel equation based on Fowller–Guggenheim equation was used to calculate the long range electrostatic interaction of the ions. The UNIFAC-NRF model was applied to correlate the experimental data of aqueous two-phase systems: PEG–K₂HPO₄–water and PEG–Na₂SO₄–water for two different molecular weight of PEG at different pH. The results of the new model showed that it can be used to correlate the LLE in aqueous solution of polymer–salt very well.