


Vol 63, No 7 (2018)
- Year: 2018
- Articles: 23
- URL: https://journal-vniispk.ru/0036-0236/issue/view/10300
Synthesis and Properties of Inorganic Compounds
Tin Acetylacetonate as a Precursor for Producing Gas-Sensing SnO2 Thin Films
Abstract
To expand the range of precursors used in the sol–gel technology for applying nanostructured SnO2 thin films promising as components of semiconductor chemical gas sensors, the efficiency of using tin acetylacetonate solutions with various precursor concentrations was demonstrated. It was determined that finely divided SnO2 with a crystallite size of 3–4 nm (cassiterite) can be obtained by hydrolysis by atmospheric moisture in the course of solvent evaporation at room temperature. Using tin acetylacetonate solutions with various precursor concentrations for applying SnO2 thin films by dip coating to the surface of rough ceramic Al2O3-based substrates with platinum interdigital electrodes and a microheater resulted in significant differences in microstructure, continuity, thickness, and porosity of the produced coatings. In a lower-concentration (0.13 mol/L) tin acetylacetonate solution, a multilayer dense continuous SnO2 coating was applied, whereas in a higher-concentration (0.25 mol/L) solution, the formed layer comprised aggregated nanoparticles 30–60 nm in size and had much more defects and higher porosity. The sensitivity of the obtained thin-film nanostructures to the most practically important gaseous analytes: CO, H2, CH4, CO2, and NO2. The produced two-dimensional nanomaterials were shown to be promising for detecting carbon monoxide at 200–300°C in dry air.



Coordination Compounds
Tri-p-Tolylbismuth Diperchlorate and μ-Oxo-bis[(perchlorato)tri-p-tolylbismuth]: Synthesis and Structure
Abstract
Tri-p-tolylbismuth perchlorate (1) and μ-oxo-bis[(perchlorato)tri-p-tolylbismuth] (2) have been synthesized by the reaction between tri-p-tolylbismuth dibromide and silver perchlorate and its hydrate. The complexes have been studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Complex 1 is triclinic, space group Pī, Z = 4, a =10.7271(9) Å, b = 13.5585(11) Å, c = 18.1592(13) Å, α = 110.867(3)°, β = 94.944(3)°, γ = 96.888(3)°, V = 2426.3(3) Å3, ρcalcd = 1.865 g/cm3; complex 2 crystallizes in trigonal symmetry, space group R\(\bar 3\), a = 13.1157(2) Å, c = 22.1959(2) Å, γ = 120°, V = 3306.64(8) Å3, ρcalcd = 1.777 g/cm3. The bismuth atoms in the molecular structure of complex 1 have a distorted trigonal bipyramidal coordination to the apically arranged oxygen atoms of perchlorate ions (Bi–C, 2.180(5)–2.201(5) Å; Bi–O, 2.324(4)–2.355(4) Å; OBiO axial angles, 170.1(1)°, 174.5(1)°). The structure of complex 2 contains binuclear [p-Tol3Bi(ClO4)]2O molecules (Bi–O, 2.371(15), 1.9107(7) Å; OBiO axial angle, 180.0°).



Mono-, Bi-, and Trinuclear Triarylantimony Organylsulfonate Derivatives: Synthesis and Structure
Abstract
The reactions of tris(3-methylphenyl)antimony with trifluoromethanesulfonic acid and of triphenylantimony with 3,4-dimethylbenzenesulfonic acid in the presence of tert-butylhydroperoxide in ether (molar ratio of initial reagents, 3: 2: 3) have been performed to synthesize nona(3-methylphenyl)tristiboxane-1,5- diyl-bis(trifluoromethanesulfonate) CF3OSO2Sb(3-MeC6H4)3OSb(3-MeC6H4)3OSb(3-MeC6H4)3OSO2CF3. PhH (I) separated after recrystallization from a benzene–octane mixture in the form of a benzene solvate and, at an equimolar ratio of initial reagents, hexaphenyldistiboxane-1,3-diyl-bis(3,4-dimethylbenzenesulfonate) separated after recrystallization from toluene in the form of a toluene solvate 3,4-Me2C6H3OSO2SbPh3OSbPh3OSO2C6H3Me2-3,4. TolH (II). The similar reactions of tris(5-bromo-2- methoxyphenyl)antimony and tris(4-methylphenyl)antimony with 2,5-dimethylbenzenesulfonic and 3,4- dimethylbenzenesulfonic acids, respectively in the presence of tert-butylhydroperoxide (molar ratio, 1: 2: 1) lead to the formation of triarylantimony bis(arenesulfonates) (5-Br,2-MeO,C6H3)3Sb(OSO2C6H3Me2-2,5)2 (III) and (4-MeC6H4)3Sb(OSO2C6H3Me2-3,4)2 (IV). The Sb atom in the structures of complexes I–IV has a distorted trigonal bipyramidal coordination to the oxygen atoms in axial positions.



Coordination Compounds of Bivalent Metals with (Z)-4-(2-Hydroxy-5-nitrophenyl)hydrazono-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one: Crystal and Molecular Structure of C16H13N5O4
Abstract
Five novel metal coordination compounds with (Z)-4-(2-hydroxy-5-nitrophenyl)hydrazono-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (H2L) have been prepared and isolated in crystalline state. Crystal and molecular structure of H2L have been established by X-ray diffraction study. A molecule of the organic compound exists in crystal state as a nearly flat hydrazo tautomer stabilized by intramolecular hydrogen bonds. Metal coordination is tridentate chelate, which has been confirmed by IR, electronic, 1H NMR, and EPR spectroscopy and DFT/B3LYP quantum chemical modeling. Coloristic and fungicidal properties of H2L and its metal complexes have been studied.



Synthesis, Molecular, and Crystal Structure of a Complex of Pentacoordinated Zinc with Chloride Ions and Pyridine-2-Carbaldehyde Hemiacetal
Abstract
The reaction between pyridine-2-carbaldehyde and zinc chloride in wet MeCN yielded a zinc chelate complex with hemiacetal formed in situ from the hydrated pyridine-2-carbaldehyde and the second molecule of pyridine-2-carbaldehyde. According to X-ray diffraction data, the pentacoordinated environment of the zinc ion is formed by two chlorine atoms and the N,N',O-tridentate ligand. In the crystal, molecules are combined into a 3D supramolecular framework due to the intermolecular hydrogen bonds O–H···Cl, C–H···Cl, and π–π stacking interactions between pyridine rings.



Synthesis, Crystal, and Molecular Structure of Bis(thiosemicarbazide)zinc(II) 1,5-Naphthalenedisulfonate Monohydrate [Zn(Tsc)2](1,5-Nds) · H2O
Abstract
Complex [Zn(Tsc)2](Nds) · H2O (I) (Tsc is thiosemicarbazide, NH2NHC(=S)NH2, and 1,5-Nds2–is the double-deprotonated anion of 1,5-naphthalenedisulfonic acid, C10H6(SO3)22-) has been synthesized and studied by IR spectroscopy, thermogravimetry, and X-ray diffraction analysis. The structural units of crystal I are complex cations [Zn(Tsc)2]2+, anions (Nds)2–, and crystallization water molecules. The Zn atom is coordinated along the vertices of the distorted tetrahedron by two sulfur atoms and two nitrogen atoms of two bidentate chelate (S,N) Tsc ligands. The structural units of crystal I are joined together by a branched network of the N–H···O hydrogen bonds involving independent donor hydrogen atoms of the NH2 and NH groups of Tsc molecules (nine of ten, except for the H(6A) atom), all six independent acceptor oxygen atoms of the SO3 groups of the Nds2– anions, and two acceptor hydrogen atoms and one donor oxygen atom of the water molecule.



Hydrated Dodecatungstatosilicate Complex with Protonated 1,2-Phenylenediamine (C6H9N2)3(H3O)SiW12O40 · 8H2O: Synthesis and Crystal Structure
Abstract
The hydrated dodecatungstatosilicate complex with protonated ortho-phenylenediamine (C6H9N2)3(Н3O)SiW12O40 · 8H2O has been synthesized and studied by X-ray diffraction. Crystals are triclinic, space group Р-1, a = 13.6817(5) Å, b =1 4.5915(5) Å, с = 15.8844(5) Å, α = 98.891(3)°, β = 101.836(3)°, γ = 114.156(2)°, V = 2729.05(16) Å3, ρcalcd = 4.100 g/cm3, Z = 2.



Synthesis and Crystal Structure of Tetrakis(dimethyl sulfoxide)copper(II) Hexafluorosilicate
Abstract
A new complex of composition [Cu(DMSO)4SiF6] (I), where DMSO is dimethyl sulfoxide (CH3)2SO, has been prepared and characterized by X-ray diffraction. Crystals I are triclinic, space group P\(\bar 1\), Z = 2, a = 10.1772(4) Å, b = 10.3061(5) Å, c = 10.6071(5) Å, V = 1003.94 Å3, ρcalc = 1.714 g/cm3.



Theoretical Inorganic Chemistry
Quantum-Chemical Modeling of B32 Complexes with Nitrogen: Endo or Exo?
Abstract
Computational modeling of borospherene B32 complexes with nitrogen has been performed by the density functional theory method (DFT UB3LYP*/6-311+G(d)). The geometry of isomers of these complexes with a different starting orientation of N has been found, their relative energies have been calculated, and the spin density distribution has been studied. Computation results predict that the structures with a nitrogen atom or ion built into the boron cage are more favorable than the endohedral isomers.



Theoretical Study of Substituent Effect in Aryl Group Migration in (para-C6H4X)Mn(CO)5 Complexes
Abstract
In this study, we report substituent effect on aryl group migration in (para-C6H4X)Mn(CO)5 complexes using mpw1pw91 quantum chemical calculations. These calculations reveal good linear relationships between barrier energy (ΔE), activation energy (ΔH‡), activation free energy (ΔG‡) values and rate constants with Hammett constants of X-substituents. The occupancy values of Mn–COcis and Mn–C(O)-(para-C6H4X) bonds in reactant, transition state and product were calculated by Natural bond orbital (NBO) method.



Structural Changes in the Macrocycles of Tetrathioand Dithiodioxo-Substituted 1,8-Dioxa-3,6,10,13-tetraazacyclotetradecane Caused by Complexation with 3d M(II) Ions according to Quantum-Chemical DFT Calculation
Abstract
The bond angles in the macrocycles of tetrathio- and dioxodithio-substituted 1,8-dioxa-3,6,10,13-tetraazacyclotetradecanes and their Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the ligand donor sites, formed upon the complexation in the ternary systems M(II)–ethanedithioamide H2N–C(=S)–C(=S)–NH2 (thiocarbamoylmethanamide H2N–C(=S)–C(=O)–NH2)–formaldehyde H2C(=O) in gelatin-immobilized matrix implants have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. It has been stated that, depending on the nature of M(II) and macrocyclic ligand, the complexation can lead to both the decrease and the increase in the degree of macrocycle distortion (quantatively characterized as the degree of deviation of the macrocycle from coplanarity).



The Influence of Chemical Composition of Fullerenes on the Structural Features and Conformational Preference of Encapsulated Disilane Molecule
Abstract
The study of the structure and conformational properties of the disilane molecule in the C80 and B47N33 fullerene cavities using the PBE/3ζ DFT method showed that the encapsulated molecule contains a shortened Si–Si bond, carries a certain electric charge, and exhibits a noticeable increase in the potential barrier to rotation around the Si–Si bond. At the same time, in the case of fullerene Si60, the observed effects, with the exception of the electric charge on the guest molecule, do not appear. For the Si2H6@C60 system, in the course of geometry optimization, a virtual reaction of disilane with the carbon skeleton of the nanoobject occurs with Si–Si bond cleavage and the formation of two SiH3 fragments bonded to fullerene carbon atoms.



Physical Methods of Investigation
Immobilization of Platinum(II) and Platinum(IV) Complexes on Oxidized Nanoporous Carbon Material and Evaluation of the Enthalpy of Adsorption
Abstract
Physicochemical study of cis-[Pt(NH3)2Cl2] and cis-[Pt(NH3)2Cl2(OH)2] is carried out, and immobilization of platinum complexes on the nanoporous carbon substrate is investigated. The solubility of cis-[Pt(NH3)2Cl2] in 1 M HCl solution is determined, and the average enthalpy of dissolution is calculated: ΔsolH° = 27.3 ± 0.9 kJ/mol. The batch capacity is determined experimentally for cis-[Pt(NH3)2Cl2] and cis- [Pt(NH3)2Cl2(OH)2] to be 32.9 mg/g (0.17 mg-equiv/g) and 47.6 mg/g (0.24 mg-equiv/g), respectively. Immobilization of platinum complexes on the oxidized carbon surface is found to take place due to interaction between carboxy groups and ammine groups of platinum complexes. The resulting heat capacity curves are used to calculate the enthalpies of adsorption for cis-[Pt(NH3)2Cl2] and cis-[Pt(NH3)2Cl2(OH)2] on the oxidized carbon surface, equal to 24.46 and 27.46 kJ/mol, respectively.



Charge Transfer and Defect Structure in BaCeO3
Abstract
Electrical conductivity (at 460–990°С) and ion and proton transference numbers (at 550–950°С) of nominally undoped BaCeO3 have been studied as dependent on temperature, pO2 (2.1 × 10–4 to 10–15 Pa), and pН2O (40–2340 Pa). For determining the defect model, small additives of aliovalent dopants Nd3+ (up to 1 at %) and Ta5+ (up to 0.5 at %) were used. The effect of cationic nonstoichiometry of barium cerate on the electrical conductivity and reaction with the gas phase has been considered. Charge transfer in ВаСеО3 is explained using the model of defect formation in the reaction of ВаСеО3 with the gas phase.



Physicochemical Analysis of Inorganic Systems
Phase Complex of the System Na,K,Mg,Ca∥SO4,Cl–H2O at 50°С in the 2MgCl2 · CaCl2 · 12H2O and CaCl2 · 2H2O Crystallization Fields
Abstract
The phase complex of the system Na,K,Mg,Ca∥SO4,Cl–H2O at 50°С in the 2MgCl2 · CaCl2 · 12H2O and CaCl2 · 2H2O crystallization fields has been predicted and constructed using the translation method. 2MgCl2 · CaCl2 · 12H2O and CaCl2 · 2H2O are involved in the formation of the following numbers of geometric images of the title system: three and one invariant points; 10 and 4 monovariant curves; and 12 and 6 divariant fields, respectively. The phase complex of the title system has been fragmented into divariant fields.



Ternary Reciprocal System K, Pb∥Cl, WO4
Abstract
The phase diagram of the ternary reciprocal system K, Pb∥Cl, WO4 was studied for the first time by the calculation–experimental method and differential thermal and X-ray powder diffraction analyses. Chemical interactions between components were described, metathesis and complexation reactions were revealed, and the coordinates of binary and ternary eutectics were found (mol %): e4(410°C, 48% KCl, 52% PbCl2), e5(424°C, 23% KCl, 77% PbCl2), P(490°C, 63.5% KCl, 36.5% PbCl2), e6(487°C, 91% PbCl2, 9% PbWO4), e7(428°C, 30.5% KCl, 60.5% PbCl2, 9% PbWO4) (eutectic in the stable section D2–PbWO4), e8(650°C, 80% KCl, 20% PbWO4), e9(650°C, 70% KCl, 15% K2WO4, 15% PbWO4) (binary eutectic in the stable section D1–KCl), E1(620°C, 59% KCl, 34% K2WO4, 7% PbWO4), E2(640°C, 75% KCl, 5% K2WO4, 20% PbWO4), E3(400°C, 46% KCl, 6% PbWO4, 48% PbCl2), E4(410°C, 21% KCl, 9% PbWO4, 70% PbCl2), and Pо(468°C, 56% KCl, 10% PbWO4, 34% PbCl2).



Phase Equilibria in the System LiF–KI–KF–K2CrO4
Abstract
Phase equilibria were experimentally studied in the system LiF–KI–KF–K2CrO4, which is the stable tetrahedron of the quaternary reciprocal system Li, K∥F, I, CrO4. Differential thermal analysis revealed the compositions and transformation temperatures at the eutectic point E□ 488 (L ⇄ LiF + KF + KI + α-K2CrO4) and the peritectic point P□ 510 (L + K3FCrO4 ⇄ KI + α-K2CrO4 + KF). A computer model of the phase complex of the system was built, which can predict phase transformations at an arbitrary composition in the system. Isothermal sections of the systems were constructed, using which the phase composition at the temperature of the section can be calculated.



Glass Formation in the Ternary System La2O3–As2S3–Er2O3
Abstract
The boundaries of the glass formation region in the ternary system La2O3–As2S3–Er2O3 were found. Transparent glass of composition (La2O3)0.03(As2S3)0.90(Er2O3)0.07 was studied by X-ray photoelectron and Raman spectroscopy. The intensities of the bands characterizing As–S, La–O, and Er–O bonds increased, and these bands were shifted toward higher energies. This was due to an increase in the covalence of these bonds and probably due to the formation of new bonds in the glasses. Samples in the glass formation region are resistant at 300 K to air, water, and organic solvents.



T–x–y Diagram of the MgO–SiO2–Al2O3 System: Computer Model Assembly
Abstract
A computer phase diagram model is constructed for the MgO–SiO2–Al2O3 system, giving its complete geometric description and containing 10 liquidus surfaces, a liquid–liquid phase separation surface, 75 ruled surfaces at the boundaries between two-phase and three-phase fields, 11 horizontal four-simplex at invariant temperatures, 21 two-phase fields, and 30 three-phase fields. The description of surfaces and three-phase fields is presented.



Determination of Cobalt in the Form of an Ion Associate in Vitamin B12
Abstract
The possibility of application of the ion-associated complex formed between the anionic chelate cobalt(II)-4-(2-thiazolylazo) resorcinol (TAR) with the cation of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) for extraction-spectrophotometric determination of cobalt in the form of an ion associate in Vitamin B12 was studied. The liquid–liquid extraction system Co(II)-TAR-MTT-H2O-CHCl3 was applied. This system was chosen by our previous research of the ion associates of the cobalt by spectrophotometric investigation of fourteen different liquid–liquid extraction systems, containing azo derivatives of resorcinol (TAR or 4-(2-pyridylazo) resorcinol (PAR)) and mono or ditetrazolium salts. Based on the obtained results, a sensitive, relatively simple, convenient and inexpensive method for determination of cobalt in the form of an ion associate in Vitamin B12 was developed. The proposed method can be implemented for biological, medical and pharmaceutical samples containing cobalamin (Vitamin B12).



Physical Chemistry of Solutions
On Gold(I) Thiomalate Complexes in Aqueous Solution
Abstract
Certain equilibria involving polymeric gold(I) thiomalate complexes have been studied by spectrophotometry and pH measurements in aqueous solution at 25°С and I = 0.2 M (NaCl). Thiomalate protonation constants Hi–1Tm3– + H+ = HiTmi–3 have been found to be logKH1 = 10.23, logKH2 = 4.51, logKH3 = 3.01. Efficient functions have been used to allow for multiple protonation of polymeric complexes Aun Tmmn-3 m Equilibrium constants for reactions Au4Tm48− + Tm3– = Au4Tm511− (logK45 = 10.1 ± 0.5) and 0.25 Au4Tm48− + Tm3– = AuTm25− (logK12 = 4.9 ± 0.2) have been determined. Standard potential for AuTm25− has been found to be equal to E1/00 =–0.260 ± 0.025 V.



Immiscibility of Liquid Phases and Liquid–Liquid Critical Phenomena in Aqueous Solutions of Sodium and Potassium Phosphates
Abstract
Phase equilibria were studied in aqueous solutions of sodium and potassium phosphates at elevated temperatures (to 425°C) and pressures (to 63 MPa). Experimental data were obtained on the transformation of gas–liquid equilibria into heterogeneous equilibria of two liquid phases with increasing pressure, which ends in the critical phenomena of immiscibility (L1 = L2). Based on the experimental and literature data, it was concluded that the binary water–salt systems containing KH2PO4, K2HPO4, K3PO4, NaH2PO4, and Na2HPO4 are characterized by phase diagrams of the first type [1, 2], which have two critical invariant end points: N (G–L1 = L2) and R (G = L1–L2).



Complexing Properties of 3-Substituted-2-(aryl-, methyl)sulfonylamino-4,5,6,7-tetrahydrobenzo[b]thiophenes with Nonferrous Metal Ions in Ammonia Media
Abstract
The complexation of 3-substituted-2-(aryl-,methyl)sulfonylamino-4,5,6,7-tetrahydrobenzo[ b]thiophenes with Cu(II), Co(II), and Ni(II) ions in ammonia media was studied. Different types of complexes with Cu(II) ions were found depending on pH: with a ratio of 1: 2 at pH of ~4–5 and 1: 1 at pH of ~ 8–10. For the Co(II) and Ni(II) ions, the formation of 1: 1 complexes at pH of ~9–10 was established. The Cu(II), Co(II), and Ni(II) complexes [Cu(HL)2. 2H2O] and [ML. 2H2O] were separated and identified, and their solubility products were calculated. The effect of the nature of the functional group in the third position of the thiophene ring on the properties of the complexes of reagents with nonferrous metal ions was shown.


