Composition and structure of heteroassociates formed in a binary liquid system HF-CH<Subscript>3</Subscript>CN

The concentration dependence of normalized absorbance (to the total number of moles of components in one liter) of HF solutions in acetonitrile (1:12–10:1) is analyzed. It is found that in the binary liquid system (BLS) under study molecular complexes with stoichiometric 1:1 and ～10:1 ratios of molecules occur along with the heteroassociates (HAs) found previously with the ratio HF:CH₃CN of 4:1. For each of the HAs the concentration range at which it is formed in BLS is evaluated, and the positions of HF stretching vibrational bands are found. Optimum configurations and vibrational frequencies of molecular complexes (HF) _m ·(CH₃CN) _n (m = 1–6, n = 1–2) of various topology are calculated using the density functional method (B3LYP/6-31 ++ G (d, p)). Their relative stability and the structure peculiarities are studied; complexation tendencies in the HF-CH₃CN system are revealed. The structure of HAs with 1:1 and 4:1 stoichiometric ratios of molecules is determined by comparing the results of calculations and experiment.     

Structure of (DMF)<Subscript>m</Subscript>(HCl)<Subscript>n</Subscript> complexes (<Emphasis Type="Italic">m</Emphasis>= 2, <Emphasis Type="Italic">n</Emphasis> = 3–4)

(DMF)₂(HCl)₃ and (DMF)₂(HCl)₄ heterocomplexes were studied for the first time in terms of the B3LYP/6-31++G(d, p) density functional calculation. The resulting data about their structure, stability, strength of intermolecular bonds, and degree of proton transfer in O...H...Cl bridges are compared with the results of a similar calculation fulfilled for (DMF)_m(HCl)_n clusters (m, n = 1–2) and with the experimental data on the structure and properties of acid-base complexes in DMF solutions of HCl. An extremely stable symmetrical cycle of four molecules — (DMF)₂(HCl)₂ — is assumed to be a structure-forming element of solution in the DMF-HCl system in the range of concentrations achievable under normal conditions. When [HCl]₀ > [DMF]₀, the “excess” hydrogen chloride molecules add to the chlorine atoms of this cycle, forming heterocomplexes with a branched structure. Addition of more HCl molecules to the (DMF)₂(HCl)₂ cycle appreciably increases the degree of proton transfer from acid to base molecule.     

Mass Spectrometric Detection of Charged Silver Nanoclusters with Hydrogen Inclusions Formed by the Reduction of AgNO<Subscript>3</Subscript> in Ethylene Glycol

In the problem of the production silver nanoparticles, mass spectrometry allows one to identify nanoclusters as nuclei or intermediates in the synthesis of nanoparticles and to understand the mechanisms of their formation. Using low-temperature secondary emission mass spectrometry, we determined the cluster composition of a system formed in the microwave treatment of a solution of AgNO₃ in ethylene glycol (M). Along with silver ion–ethylene glycol associates М _m ? Ag⁺ (m = 1–5) and small silver clusters AgM _n ⁺ (n = 1–9), unusual silver clusters with one hydrogen atom [Ag _n H]⁺ (n = 2, 4) were observed. Possible pathways for the formation of silver nanoparticles taking into account hydrogen-containing cluster intermediates are discussed.     

Solubility of <Emphasis Type="Italic">d</Emphasis>-Element Salts in Organic and Aqueous–Organic Solvents: VI.<Superscript>1</Superscript> Structure and Thermal Stability of Cadmium Iodide and Bromide Solvates with Dimethylacetamide and Dimethylformamide

Five solvates, [CdBr₂(DMF)] _n , [CdBr₂(DMA)] _n , [CdI²(DMF)] ⁿ , [Cd(DMF)₆][Cd₂I₆], and {[Cd(DMA)₆][Cd₅I₁₂] _n } _m , were isolated from the ternary systems CdX₂–L–H₂O (X = Br, I; L = N,N-dimethylacetamide, N,N-dimethylformamide) and characterized by the X-ray single crystal analysis. The structures of the first three solvates is similar to each other in structures and represent a one-dimensional polymer chain, the fourth solvate has the discrete structure containing [Cd(DMF)₆]²⁺ and [Cd₂I₆]^2– ions, and the fifth solvate contains discrete [Cd(DMA)₆]²⁺ cations and the polymer anionic fragment [Cd₅I₁₂] _n ^2n–.     

Electronic Structure and Relative Stabilities of 10- and 12-Vertex. <Emphasis Type="Italic">Closo</Emphasis>and <Emphasis Type="Italic">Nido</Emphasis>-Heteroborane Clusters of Ga,Ge, and As Elements

A DFT method with the B3LYP functional and the 6-311++G(d,p) diffuse basis set is used to predict geometries, relative stabilities, electronic structures, and the bonding of closo- and nido-Ga_mB_n–mH _n ^2? , Ge_mB_n–mH _n ^m?2 , and As_mB_n–mH _n ^{2 m?2} (n = 10, 12 and m = 1, 2) Clusters are obtained by replacing BH with isolobal GaH, GeH⁺, and AsH²⁺ fragments, keeping the same skeleton electron pairs (SEP). Based on the polyhedral skeletal electron pairs theory (PSEPT), closo and nido structures are predicted and can be of significant interest for experimentalists working in the field of heteroboranes. Different cluster stabilities are studied according to Gimarc′s and Williams′ rules, where our calculations show that the monosubstituted clusters deviate from these rules, giving rise to open structures. As₂B₈H _n ²⁺ as 10-vertex structures lead to nido-type clusters, however, Ge_mB_n–mH _n ^m?2 (n = 10, 12 and m = 1, 2) give rise to closo isomers with close energies. All optimized structures exhibit large HOMO–LUMO gaps suggesting a good kinetic stability, thus predicting their isolation and characterization.     

DFT study of small aluminum and boron hydrides: isomeric composition and physical properties

The structure, energetics, and physical properties, including rotational constants, characteristic vibrational temperatures, dipole moment, static polarizability, HOMO-LUMO gap, formation enthalpy and collision diameter of different isomeric forms of atomic Al _n H _m and B _n H _m clusters with n = 1..4 and all feasible m numbers are studied within the density functional theory framework. The search of isomer structures has been accomplished using multistep hierarchical algorithm. Temperature dependences of thermodynamic functions (enthalpy, entropy and specific heat capacity) have been calculated both for the individual isomers and for the ensemble of isomers with equilibrium composition for each class of clusters, taking into account the anharmonicity of cluster vibrations and the contribution of excited electronic states. The prospects of the application of small atomic Al _n H _m and B _n H _m clusters as the components of energetic and hydrogen storage materials are also discussed.     

Three alkaline earth metal-organic frameworks based on fluorene-containing carboxylates: syntheses,structures and properties

Three metal-organic frameworks,{[Mg_2(MFDA)_2(DMF)_3]·0.5H_2O}_n(1),{[Ca(MFDA)(DMF)(H_2O)]·0.5DMF}_n(2)and[Ca(MFDA)(DMF)_2]_n(3)(DMF=N,N-dimethylformamide)have been synthesized by the solvothermal reactions between the ligand 9,9-dimethylfluorene-2,7-dicarboxylic acid(H_2MFDA)and the corresponding metal salts,respectively.The single crystal X-ray structural analyses reveal that compounds 1-3 display three-dimensional structures based on the M(Ⅱ)-O-C chains.It is interesting that the MFDA ligands in 1-3 have different dihedral angles between the two carboxylate groups ranging from 9.9(1)°to 41.8(2)°.All of compounds exhibit strong ligand-centered blue emissions under UV lights.Their thermal properties have also been studied.     

New approach to the synthesis of linear and cyclic vinyl(alkoxy)siloxanes

Main products of the reaction of vinyltrichlorosilane VinSiCl₃ with DMSO in the medium of tetra-(alkoxy)silane are linear siloxanes (RO)₃Si[OSiVin(OR)]OSi(OR)₃, RO[Vin(RO)SiO] _n Si(OR)₃ (R = Me, Et, n = 0–2) and the hitherto unknown cyclic siloxanes [Vin(RO)SiO] _m [(RO)₂SiO]_4–m (m = 1–3) formed in the ratio of 70: 30%. A tentative scheme of their formation is suggested with participation of the products of the alkoxy groups exchange between vinyl(alkoxy)dichloro-, vinyldi(alkoxy)chloro-, trialkoxychloro-, and dialkoxydichlorosilanes.     

Molecular structure investigation of Z-3N(2-ethoxyphenyl)-2-N′(2-ethoxyphenyl)-imino-thiazolidin-4-one by <Emphasis Type="Italic">ab initio</Emphasis>, DFT and X-ray diffraction methods

We report here the synthesis of the Z-3N(2-ethoxyphenyl)-2-N′(2-ethoxyphenyl)-imino-thiazolidin-4-one compound. The crystal structure is determined by X-ray diffraction. The compound crystallizes in the monoclinic system with the space group P2_1/n and cell parameters: a = 9.4094(10) Å, b = 9.3066(10) Å, c = 20.960(2) Å, β = 99.0375(10)°, V = 1812.7(3) ų and Z = 4. The structure is refined to final R = 0.05 for 2083 observed reflections. The molecule in the crystal exhibits the intermolecular hydrogen bonds of C–H…O, C–H…N, and C–H…S types. Ab initio calculations are also performed at Hartree–Fock (HF) and density functional theory (DFT) levels. The full HF and DFT geometry optimization is carried out using the 6-31G(d,p) basis set. The observed molecular structure is compared with that calculated by both HF and DFT methods. The optimized geometry of the titled compound is found to be consistent with the structure determined by X-ray diffraction.     

The influence of sodium trifluoroacetate on the acidity function of solutions of trifluoroacetic acid in N,N-dimethylformamide

The influence of CF₃COONa on the acidity function (H ₀) and IR spectra of the CF₃COOH-N,N-dimethylformamide (DMF)-CF₃COONa system ([CF₃COOH] ≤ [DMF], [CF₃COONa] = 0–3 M) and H ₀ of solutions of the salt in 100% CF₃COOH ([CF₃COONa] = 0–1.2 M) was studied. The addition of the salt to 100% CF₃COOH insignificantly changed solution acidity; H ₀ passed a minimum at [CF₃COONa] = 0.7 M because of the formation of (CF₃COO…H…OOCCF₃)^? anions and destruction of acid associates in the presence of the salt. Changes in the acidity of solutions of CF₃COOH in DMF caused by the addition of the salt depended on the n = [CF₃COOH]/[DMF] ratio. At n = 1, the salt almost did not influence H ₀. At n < 1, a substantial decrease in the acidity of solutions was observed, because the salt increased the degree of proton transfer in CF₃COO…H…OC(H)N(CH₃)₂ quasi-ion pairs solvated by DMF molecules.     

Chemistry of the CARBOFTOREX process. Identification of the absorption bands of the ligands in the electronic spectra of aqueous solutions of U(VI) fluoride carbonate complexes

The electronic absorption bands of U(VI) fluoride carbonate and fluoride hydroxide complexes were assigned taking account of dissociation, hydration, association, and ligand exchange. The absorption in the range of 190–400 nm was found to be related to the formation of neutral and dissociated anionic U(VI) fluoride carbonate and fluoride hydroxide complexes and the polynuclear Na_2n [(UO₂–O–UO₂)F₄(OH)_2n–1 ? kH₂O] complex.     

Crystal Structure of <Emphasis Type="Italic">DL</Emphasis>-Valinium Tetrafluoroantimonate(III) Monohydrate

The crystal structure of an antimony(III) fluoride complex of the composition (C₅H₁₂NO₂)SbF₄·H₂O (I) involving a cation of α-amino isovaleric acid (DL-valine, Val) is determined. Crystals are monoclinic: a = 12.2024(2) Å, b = 6.1636(1) Å, c = 15.5167(3) Å, Z = 4, space group P2₁/c. The structure is formed of DL-valinium (C₅H₁₂NO₂)⁺ cations, complex [SbF₄]_n^n? anions having a polymeric chain structure, and crystallization water molecules. The [SbF₄]_n^n? complex anions consist of trigonal SbF4E bipyramids joined together by asymmetric bridging Sb–F(3)···Sb bonds. The structural units are organized into a threedimensional framework via N–H···F, N–H···O, and O–H···F hydrogen bonds.     

Synthesis and magnetic properties of quasi-unidimensional oxide Sr<Subscript>6.3</Subscript>Rh<Subscript>2.35</Subscript>Mn<Subscript>2.35</Subscript>O<Subscript>15</Subscript>

Attempts of the synthesis in air of complex oxides Sr₃RhMnO_x and Sr₄Rh_1.5Mn_1.5O_x resulted in revealing formation of a new oxide phase Sr_6.3Rh_2.35Mn_2.35O₉ related to quasi-unidimensional family A_3n+3m A′ _n B_3m+n O_9m+6n at n = 1 and m = 1. Its structural characteristics and magnetic properties are studied. X-ray data of the obtained phase is indicated on the basis of trigonal cell (spatial group P321) with the parameters: a 9.6239(4) Å; c ₁ 4.1130(4) Å, c ₂ 2.4946(2) Å. Manganese and rhodium exist in the compound as the cations Mn⁴⁺, Rh³⁺ and Rh⁴⁺, as follows from the data of measuring of magnetic susceptibility in the range 2–300 K.     

Estimating the energy of intramolecular hydrogen bonds in chitosan oligomers

The effect the number of chitosan monomer units CTS_n (n = 1–5), the protonation of chitosan dimers, and the interaction between CTS_n (n = 1–3) and acetate ions have on the energy of intramolecular hydrogen bonds is investigated by means of QTAIM analysis and solving the vibrational problem within the cluster-continuum model. It is established that the number of H-bonds in CTS_n is 2n ? 1 and the total energy of H-bonds grows by ~20 kJ/mol. It is concluded that the hydrogen bonds between CTS and acetate ions play a major role in the stabilization of polyelectrolyte complexes in dilute acetic acid solutions of CTS.     

On hydrolysis of Ba–Bi–O and K–Ba–Bi–O oxide systems

Fundamentally different behavior of Ba–Bi–O (Ba : Bi = 11 : 4, 1 : 1, 2: 3, and 1 : 5 mol/mol) and K_nBa_mBi_m+nO_y (m = n = 1, 2,...; exhibiting superconducting properties with T_c = 28–32 K) oxides and BaO₂ in hydrolysis reactions has been revealed by means of potentiometry and chemical analysis. Products of the oxides treatment with water do not contain H₂O₂, evidencing the absence of peroxide ions in their structure. The perovskite-type barium-bismuth(III) oxides are completely hydrolyzed into Ba(OH)₂ and Bi₂O₃ at room temperature.     

Hydrogen-Bonding Interaction in a Complex of Amino Acid with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylformamide Studied by DFT Calculations

Theoretical studies on hydrogen-bonded complexes between amino acids (glycine, alanine and leucine) and N,N-dimethylformamide (DMF) in gas phase have been carried out using density functional theory (DFT) and ab initio calculations at the B3LYP/6-311++G** and MP2/6-311++G** theory levels. The structures, binding energy, stretching frequency and bond characteristics of the mentioned complexes were calculated. The NH₂ and COOH groups of amino acids form different types of hydrogen bonds with the DMF molecule, as well as alkyl side chains. High binding energy suggests multiple hydrogen bonds present in one complex. The nearly linear OH???O and NH???O contacts are stronger than a conventional hydrogen bond interaction with their H???O separation between 1.74 and 2.14 Å. The weaker CH???O H-bond is also discussed as being a crucial interaction in biological systems involving amino acids. The formation of this interaction results in a blue shift in the CH stretching frequency.     

Effect of catalyst structure on the reaction of α-methylstyrene with 1,1,3,3-tetramethyldisiloxane

Reaction of α-methylstyrene with 1,1,3,3-tetramethyldisiloxane in the presence of the complexes of platinum(II), palladium(II) and rhodium(I) is explored. It is established that in the presence of platinum catalyst predominantly occurs hydrosilylation of α-methylstyrene leading to formation of β-adduct, on palladium catalysts proceeds reduction of α-methylstyrene, on rhodium catalysts both the processes take place. In the reaction mixture proceeds disproportion and dehydrocondensation of 1,1,3,3-tetramethyldisiloxane that leads to formation of long chain linear and cyclic siloxanes of general formula HMe₂Si(OSiMe₂) _n H and (-OSiMe₂-)m (n = 2–6, m = 3–7), respectively. Platinum catalysts promotes formation of linear siloxanes, while both rhodium and palladium catalysts afford linear and cyclic siloxanes as well. Structure of intermediate metallocomplexes is studied.     

DFT study on oxidation of HS(CH<Subscript>2</Subscript>)<Subscript> <Emphasis Type="Italic">m</Emphasis> </Subscript>SH (<Emphasis Type="Italic">m</Emphasis> = 1–8) in oxidative desulfurization

Density functional theory was employed for calculation of HS(CH₂)_mSH (m = 1–8) and its derivatives at B3LYP method at 6-31++g (d,p) level. Using eigenvalues of LUMO and HOMO for HS(CH₂)_mSH, the standard electrode potentials were estimated by a stepwise multiple regression techniques (MLR), and obtained as E° = 1.500 + 7.167 × 10^–3 HOMO–0.229 LUMO with high correlation coefficients of 0.973 and F values of 43.973.     

Heat capacities and thermal diffusivities of <Emphasis Type="Italic">n</Emphasis>-alkane acid ethyl esters—biodiesel fuel components

The heat capacities and thermal diffusivities of ethyl esters of liquid n-alkane acids C _n H_2n–1O₂C₂H₅ with the number of carbon atoms in the parent acid n = 10, 11, 12, 14, and 16 are measured. The heat capacities are measured using a DSC 204 F1 Phoenix heat flux differential scanning calorimeter (Netzsch, Germany) in the temperature range of 305–375 K. Thermal diffusivities are measured by means of laser flash method on an LFA-457 instrument (Netzsch, Germany) at temperatures of 305–400 K. An equation is derived for the dependence of the molar heat capacities of the investigated esters on temperature. It is shown that the dependence of molar heat capacity C _p,m (298.15 K) on n (n = 1–6) is close to linear. The dependence of thermal diffusivity on temperature in the investigated temperature range is described by a first-degree polynomial, but thermal diffusivity a (298.15 K) as a function of n has a minimum at n = 5.     

Structural characterization of a mixed-ligand complex of copper(II) with 1,10-phenanthroline and the <Emphasis Type="Italic">m</Emphasis>-aminobenzoate ion

A new copper(II) complex of 1,10-phenanthroline (C1₂H₈N₂) and the meta-aminobenzoate ion (m-amb; C₇H₆NO ₂ ^? ), having the formula Cu(C₁₂H₈N₂)(C₇H₆NO₂)Cl?0.5H₂O, is prepared and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. The structure is built up from monomeric units in which the coordination environment around the metal ion is a square plane arising from a bidentate 1,10-phenanthroline molecule, a monodentate m-amb anion, and a chloride ion. A very long (Cu–N = 2.856(5) Å) bond to the nitrogen atom of an adjacent m-amb ion generates [101] polymeric chains in the crystal. The crystal structure is consolidated by N–H???O and O–H???O hydrogen bonds and C–H???O, C–H???Cl, and aromatic π–π stacking interactions. Crystal data: C₁₉H₁₅ClCuN₃O_2.5, M _r = 424.33, monoclinic, P2₁/n (No. 14), a = 9.8200(5) Å, b = 10.9291(7) Å, c = 16.3803(9) Å, β = 105.293(3)°, V = 1695.74(17) ų, Z = 4, R(F) = 0.043, wR(F ²) = 0.122.