On template synthesis in the ternary system Ni(II)-thiosemicarbazide-diacetyl

A new complexation process in the ternary system Ni(II)-hydrazinomethanethioamide (thiosemicarbazide)-2,3-butanedione (diacetyl) has been studied. Complexation occurs in an aqueous ethanol solution and in nickel(II) hexacyanoferrate(II) gelatin-immobilized matrix systems. It has been shown that, under these conditions, the process involves the “self-assembly” (template synthesis) of Ni(II) macrotricyclic complexes with a new chelating ligand—4,5-dimethyl-1,8-dimercapto-2,3,6,7-tetraaza-1,3,5,7-octatet-raene-1,8-diamine with the (NSSN) coordination of donor atoms to the metal atom.     

IR spectral and quantum-chemical studies of binary extractants

The composition and ionic character of formation of binary extractants based on quaternary ammonium bases and organic acids were confirmed using spectral and quantum-chemical methods, the structures of the binary extractants were obtained. The energy of bond between cation and anion in molecules of the binary extractants was determined, it is by an order of magnitude higher than the energy of H bond and close to the energy of chemical (ionic) bond.     

Solvation and microdynamics of uranium(IV) in 2LiF-BeF2 melts according to molecular dynamics calculations

The structural features of solvation and diffusion characteristics of U(IV) ion in model 2LiF-BeF₂ melts (Flibe) at 750–1600 K have been studied by the molecular dynamics simulation method. The diffusion activation energy of U(IV) ion in the 2LiF-BeF₂ melt has been calculated.     

Platinum nanoparticles on the antimony-doped tin dioxide surface: Quantum-chemical modeling

The interaction of Pt₂₉ nanoparticles with pristine and reduced (110) and (100) SnO₂ surfaces doped with Sb has been modeled using the density functional theory method within the generalized gradient approximation (GGA). It has been demonstrated that the introduction of antimony contributes to dispersion of substrate particles and, in some cases, leads to an increase in the energy of interaction with platinum and to the fixation of platinum nanoparticles on the surface.     

Trends in formation of the nanocrystalline structure and cationic ordering in the Dy2O3-HfO2 (1: 1) system

Evolution of the nanocrystalline structure of the complex oxide Dy₂HfO₅ in the course of thermal annealing at temperatures to 1600°C has been studied by a combination of X-ray and synchrotron methods, including traditional and anomalous X-ray diffraction, PDF, EXAFS, and SAXS. The changes in crystallite size upon annealing of the as-synthesized amorphous precursor have been analyzed in detail. The systematic distortions of a fluorite-type perfect crystal structure (space group $Fm\bar 3m$ ) related to the nonequivalence of the local environment of the Dy and Hf cations but not resulting in formation of a pyrochlore-type cationordered structure in this system have been examined.     

Structure and properties of (Ac)Fe(III)-5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrin in the reaction with organic peroxides in benzene: The effect of imidazole on reaction kinetics

The kinetics of the reaction between (Ac)Fe(III)-5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrin and dicumene peroxide in benzene at 295 K was studied with the purpose of further studying the effect of the conformational and electronic factors of nonplanar metalloporphyrinates on redox properties using a combination of computational and spectrophotometric methods. The molecular structures of reagents and intermediates of the studied reaction were optimized by the PM3 quantum-chemical method. The obtained characteristics were analyzed, and the distortion of a macrocycle was established to considerably increase in the reaction of iron(III) porphyrinate with peroxides. The intermediate molecule was found to be sterically hindered and extremely unstable. The kinetic characteristics of the reaction were obtained spectrophotometrically. The nature of a metal atom and the distortion of a macrocycle were established to have some effect on the process rate. The introduction of imidazole into a reaction mixture and the variation of concentration of a base were shown to produce some changes in the composition of reagents and the kinetics of the process. A good agreement between experimental and calculated data was observed.     

Synthesis and structure of complexes of some d metals with 10-(2-benzothiazolylazo)-9-phenanthrole (HL). Crystal and molecular structures of [CdL2] · DMF

The coordination compounds of cadmium(II), zinc(II), nickel(II), cobalt(II), and copper(II) with 10-(2-benzothiazolylazo)-9-phenanthrole (HL) were isolated in the crystalline state and studied. The crystal structure of the cadmium complex [CdL₂] · DMF was determined by X-ray diffraction. The ligand is attached to cadmium in the form of anion functioning as an O,N,N-tridentate chelating ligand; this is accompanied by a change in its isomer form. The Cd configuration is a distorted octahedron.     

Synthesis and structure of the oxalatotetranitratouranylate complex (NH4)2[{UO2(NO3)2}2(μ4-C2O4)] · 2H2O

The reaction of diaquadinitratouranyl with ammonium nitrate in ethanol gave the single crystals of ((NH₄)₂[}UO₂(NO₃)₂}₂(μ₄-C₂O₄)] · 2H₂O (I).The structure of the complex was studied by X-ray diffraction. The crystals are monoclinic, a = 8.6497(10) Å, b = 11.7001(10) Å, c = 20.2135(10) Å, β = 93.924(10)°, space group P2₁/c, Z = 4, V = 2040.9(3) ų. The structural units of the crystal are island binuclear groups [{UO₂(NO₃)₂}₂(μ₄-C₂O₄)]^2?, ammonium cations, and crystal water molecules. The structure has a complex three-dimensional packing provided by electrostatic attraction forces of the counterions and the hydrogen bond system involving water molecules, oxalate, nitrate, and uranyl ions. The IR spectra of I confirm the X-ray diffraction data.     

Synthesis, crystal, and molecular structure of the solvated complex [MoO2(L)] · DMF (L2− = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol anion)

A new dioxomolybdenum(VI) complex, [MoO₂(L)] · DMF, where L^2? = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol, has been synthesized. Its structure has been determined by X-ray diffraction analysis. The Mo atom is octahedrally coordinated by two oxo ligands that are in cis-positions with respect to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) ligand L, and the DMF oxygen atom.     

Chemical interaction in the quaternary mutual systems Li,K‖F,Cl,MoO4 and Li,K‖F(Cl),VO3,MoO4

The Li,K‖Cl,VO₃,MoO₄ system was partitioned into simplexes using graph theory, and the tree of phases for this system was constructed. The equations of the main reactions describing the chemical interaction in the quaternary mutual systems Li,K‖F,Cl,VO₃(MoO₄) and Li,K‖F(Cl),VO₃,MoO₄ were derived using the conversion patterns of partitioning elements. Based on the reaction equations and the data on the boundary elements, the prediction of phases crystallizing in the studied systems was made and confirmed by X-ray powder diffraction analysis.