Том 86, № 10 (2016)
- Год: 2016
- Статей: 27
- URL: https://journals.rcsi.science/1070-3632/issue/view/13455
Article
Study of simultaneous solubility of salts in the ammonium nitrate–ammonium chloride–water system
Аннотация
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.
Thermochemical study of gaseous salts of oxygen-containing acids: XXII.1 Lead salts
Аннотация
Reactions of gas-phase synthesis of lead phosphates and tellurates have been studied. Standard enthalpies of formation and atomization of gaseous PbPO2, PbPO3, PbP2O6, PbTeO3, and Pb2TeO4 salts have been determined.
Special features of formation of nanocrystalline BiFeO3 via the glycine-nitrate combustion method
Аннотация
Nanocrystalline bismuth orthoferrite has been synthesized under conditions of glycine-nitrate combustion. Temperatures of activation of formation and growth of BiFeO3 nanocrystals have been shown to correlate with melting temperature of surface (non-autonomous) phases. Optimal temperature of synthesis of nanocrystalline bismuth orthoferrite has been determined.
Quantum-chemical approach to optimization of the synthesis conditions of two-component phosphorus-titanium oxide structures on silica surface
Аннотация
The features of formation of a two-component phosphorus-titanium oxide coating on the silica surface by sequential treatment of the substrate with POCl3 and TiCl4 vapors were analyzed with application of quantum-chemical approaches. An experimental synthesis of two-component coatings under conditions selected on the basis of theoretical calculations yielded coatings whose composition corresponded to the model predictions. The structure of the resulting coatings was studied by Fourier-transform IR spectroscopy, electronic diffuse reflectance spectroscopy, and chemical analysis.
Kinetic aspects of hydrochemical deposition of cadmium sulfide from solutions with diverse ligand backgrounds
Аннотация
A comparative kinetic study was carried out and formal kinetic equations were derived for the chemical deposition of cadmium sulfide from aqueous solutions containing various cadmium complexes onto a glass-ceramic substrate by thiourea under conditions of spontaneous nucleation and interfacial area control. The elemental composition and morphology of the resultant films were examined, on this basis their nanostructure nature was confirmed, taking into account the data on crystallite size analysis.
Formation of solid solutions of multiferroics in the Bi2O3–Nd2O3–Fe2O3 system
Аннотация
The sequence of phases appearance during the formation of Bi1–xNdxFeO3 solid solutions in powder oxides mixtures of bismuth, neodymium, and iron has been determined. It has been shown that the closeness of the reaction mixture composition to that of the individual compound (BiFeO3 or NdFeO3) is essential for the realization of the series of phase transformations yielding solid solutions of multiferroics Bi1–xNdxFeO3 as the final product, due to the prevalence of various interphase contacts in the starting reaction zone.
Estimation of electrooptical parameters of EХ3 molecules in ground and excited states from empirical correlation equations
Аннотация
Basing on the experimental data, it has been shown that for EХ3 (E = N, P, As, or Sb; X = F, Cl, Br, I, CH3, С6Н5, or SiH3) compounds the value of the difference between first ionization potentials of atoms and molecules is a function of the bond angle and dipole moment of the molecule. The calculated values of dipole moments of charged atoms and groups are regularly changed within the considered compounds series. The change of the dipole moment of the molecules during the vibrational excitation has been determined, and intensities of symmetric stretching and deformation bands in IR spectra of EF3 and ECl3 compounds have been estimated.
Alkene subspectra of monofunction compounds mass spectra: Tandem mass spectrometry investigation
Аннотация
Using the tandem mass-spectrometry method, the experimental evidence have been obtained that an important component of electron ionization mass spectra of monofunctional compounds RX (X being a functional group) is the alkene subspectrum, including peaks of fragment ion [R–H]+· and products of its fragmentation.
The effect of the coordination sphere of the platinum catalyst on the course of the direct С–С coupling in the systems PtII–ArH–ArI–base. The experimental and theoretical (DFT) study
Аннотация
The composition of coupling products in reaction of arenes with aryl iodides catalyzed with Pt(phen)Cl2, Pt(bipy)Cl2, Pt(py)2Cl2 and K2PtCl4 complexes was studied. Based on quantum-chemical calculations of the charges on platinum atoms, the energies of the frontier molecular orbitals of the metal complexes and substrates an approach is proposed to forecasting the effect of the structure of the catalyst on the direction of the reaction towards the homo or cross-coupling.
Optimized synthesis of 2-substituted 1-halocyclopropane-1-carboxylic acids
Аннотация
The reaction of gem-dichloro- and gem-dibromocyclopropanes with n-butyllithium in THF under argon at–78°С followed by purging the reaction mixture with dry CO2 was used to synthesize cis- and/or trans-1-halocyclopropane-1-carboxylic acids in 30–56% yields. The yields of the target products could be increased to 76–83% by the addition of an equimolar amount of LiCl to the reaction mixture. The highest salt effect was obtained with lithium chloride generated in situ (88–96%).
3-(4-N,N-dimethylaminophenyl)-2-nitro-1-phenylprop-2-en-1-one by 13C NMR spectroscopy and X-ray diffraction analysis
Аннотация
X-ray diffraction analysis established that 3-(4-N,N-dimethylaminophenyl)-2-nitro-1-phenylprop-2-en-1-one has E configuration both in crystal and in solution. The benzoyl group deviates from the styrene plane by 89.83°. The elongation of the C=C bond and shortening of its surrounding single bonds points to a high polarization of the molecule, implying a great contribution of the bipolar structure to the ground state.
Regioselectivity of the methanolysis of polychlorinated biphenyls
Аннотация
Regioselectivity of the methanolysis of lower polychlorinated biphenyls with sodium methoxide in a mixture of methanol and DMSO at 100–130°С was studied. It was found that 2,4,4'-tricholobiphenyl is much more reactive than 2,4-dichlorobiphenyl. This results in different mechanisms of substitution. 2,4-Dichlorobiphenyl reacts with sodium methoxide by the elimination–addition mechanism to form four monosubstitution products in comparable quantities. 2,4,4'-Trichlorobiphenyl reacts with the methodixe ion by the classical SNAr mechanism, with preferential substitution of the 2-chlorine atom.
Synthesis and antiradical activity of hybrid antioxidants based on isobornylphenols
Аннотация
Alkylation of isobornylphenols with allylbenzene in the presence of homogeneous and heterogeneous catalysts of different nature has been studied. The maximum yield of phenols containing isobornyl and 1-phenylpropyl moieties has been achieved in the presence of catalyst FIBAN K-1 at 100°С and catalyst concentration of 10%. The inhibiting action of isobornylphenol derivatives has been studied in the model reaction of ethylbenzene oxidation. Hybrid antioxidants on the basis of isobornylphenols were found to actively interact with peroxide radicals and, therefore, they can be considered as promising additives for conservation of quality and increase in service life of different organic compounds and materials.
Synthesis of substituted dihydropyridines by reacting ethoxymethylidenemalonate with malonic acid N-arylamidoesters
Аннотация
Reactions of ethoxymethylidenemalonate with malonic acid N-arylamidoesters in the presence of triethylamine afforded diethyl 1-aryl-6-hydroxy-2-oxo-1,2-dihydropyridine-3,5-dicarboxylates via the cyclization of Michael adducts. In the presence of sodium ethoxide the formed adducts may be also involved into simultaneous retro-Michael reaction leading to the formation of ethyl 1-aryl-5-arylcarbamoyl-6-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylates. Direction of heterocyclization or retro-Michael reaction is determined by the acidity of the hydrogen atoms of adducts and basicity of catalyst.
An X-ray spectral and theoretical study of the electronic structure and features of interatomic interactions in phenoxysilanes
Аннотация
The electronic structure and features of interatomic interactions providing the Si–O–C6H5 bonds in H4-nSi(OC6H5)n (n = 1–4) were studied by a combined analysis of the X-ray emission and photoelectron spectroscopic data and the results of quantum-chemical calculations. Theoretical calculations were carried out using the density functional theory. The distributions of the density of states were constructed, the correlation energy diagrams were presented, and the main types of interatomic interactions in phenoxysilanes were revealed.
Reaction of o-aminophenol and o-aminobenzyl alcohol with palladium(II) bis(isocyanide) complexes
Аннотация
Reactions of palladium(II) bis-isocyanide complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3, 2-Me-6-ClC6H3) with an equimolar amount of chelating N,O-binucleophiles, 2-aminophenol and (2-aminophenyl)-methanol, in acetonitrile at room temperature in 24 h selectively afforded the corresponding open-chain monocarbene complexes. The complexation involved one isocyanide ligand and amino group of the aromatic amine. Neither bis(carbene) complexes (in the reactions with 4 equiv of the nucleophile under harsh conditions) nor C,O-chelate structures were detected. The isolated complexes were characterized by elemental analyses, IR, NMR, and mass spectra, and X-ray diffraction data.
Synthesis and structure of gold complexes [Ph3P(4-FC6H4CH2)]+[AuCl4]– and [Ph3PCH2CH=CHMe]+[AuCl4]–
Аннотация
The reaction of tetrachloroauric acid hexahydrate with (4-fluorobenzyl)triphenylphosphonium and (buten-2-yl)triphenylphosphonium (1:1, mol) chlorides results in the formation of the [Ph3P(4-FC6H4CH2)]+ [AuCl4]– and [Ph3PCH2CH=CHMe]+[AuCl4]– complexes. Structure of the complexes was studied by the X-ray diffraction (XRD) analysis.
Coordination compounds of cobalt(II), nickel(II), and zinc(II) valerates and benzoates with benzohydrazide
Аннотация
Coordination compounds of cobalt(II), nickel(II), and zinc(II) valerates and benzoates with benzohydrazide have been synthesized and characterized by elemental analyses, IR spectra, diffuse reflectance spectra, and thermogravimetric data.
Solvation state of iron(III) in aqueous solutions of dimethyl sulfoxide. Complex formation ability of iron(III) with respect to derivatives of sym-triazine and bis(hydrazinocarbonylmethyl) sulfoxide
Аннотация
Parameters of the solvation equilibria \({\left[ {Fe{{\left( {{H_2}O} \right)}_6}} \right]^{3 + }} + nDMSO \rightleftarrows {\left[ {Fe{{\left( {{H_2}O} \right)}_{6 - n}}{{\left( {DMSO} \right)}_n}} \right]^{3 + }} + n{H_2}O\) have been determined in aqueous-dimethyl sulfoxide solutions (0–90 vol% DMSO) by means of spectrophotometry and mathematical modeling of equilibria. Iron(III) is not involved in the complex formation with derivatives of sym-triazine: 2,4-diamino-6-(carbamoylmethylsulfinylmethyl)-1,3,5-triazine and 2,4-diamino-6-(acetohydrazidomethylsulfinylmethyl)-1,3,5-triazine in aqueous DMSO medium (40 vol % DMSO). Bis(hydrazinocarbonylmethyl) sulfoxide forms two complexes with iron(III), with 1: 1 and 1: 2 compositions; in contrast to the Cu(II) and Ni(II) complexes, in the iron complexes the ligand exists in the amide form. The most probable structures of the complexes have been revealed by molecular mechanics simulation and (in selected cases) using the DFT/B3LYP/6-31++G(d,p) density functional theory method.
Characterization of Cu(II) coordination compounds with 2-(7-bromo-2-oxo-5-phenyl-2,3-dihydro-1Н-1,4-benzodiazepin-1-yl)acetohydrazide and a product of its condensation with pyruvic acid
Аннотация
[Cu(HydrHPv)(H2O)Cl2] complex has been prepared and characterized by elemental analysis, IR spectroscopy, electrical conductivity, and magnetic susceptibility data. Structure of the coordination sphere and exact parameters of nearest surrounding of Cu2+ ions have been determined by X-ray absorption spectroscopy.
Synthesis, structure, and photoluminescence properties of molecular complexes of bis(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-olato)cadmium(II) with aminoquinolines and 1-aminoisoquinoline
Аннотация
Molecular complexes of bis(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-olato)cadmium(II) with isoquinolin-1-amine, quinolin-3-amine, 4,6-dimethylquinolin-5-amine, and quinolin-6-amine have been synthesized, and their structure was studied by IR, UV, 1H NMR, and X-ray absorption spectroscopy. Photoluminescence properties of the complexes have also been examined.
Formation of iron-containing composites
Аннотация
The influence of corrosion inhibitors of different types on the formation of iron-containing composites in the presence of polyvinylpyrrolidone (PVP) and polyethyleneimine (PEI) was studied. It was shown that the composite containing sodium citrate is the most resistant to oxidation. To form the PVP‒Fe‒PEI composite in the medium containing a tea extract, no NaBH4 is necessary to be added, whereas in the presence of P. adametzii fungal culture fluid permeate the reaction medium should contain an excess of NaBH4. For aldehyde functionalization of the PVP‒Fe‒PEI composite was activated with glutaraldehyde or dextran Т20 oxidized with NaIO4.