Synthesis and Structure of a New Ruthenium(II) Clathrochelate and the Use of a Highly Porous Ceramic Material with an Immobilized Complex in the Oxidative Conversion of Methane

Kinetics and Catalysis - A new ruthenium(II) cage complex with polar terminal groups in the apical substituents has been synthesized; the molecular design of the complex contributes to the...     

Novel ligands based on bromosubstituted hydroxycarbonyl [2.2]paracyclophane derivatives: synthesis and application in asymmetric catalysis

New planar-chiral hydroxycarbonyl [2.2]paracyclophane derivatives, 4-acetyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-АНРС, 63%) and 4-benzoyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-BHPC, 53%), were synthesized and reacted with the enantiomers of α-phenylethylamine to form corresponding Schiff bases, 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-ethyl]-[2.2]paracyclophane and 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-(phenyl)methylen-[2.2]paracyclophane. The diastereomers of the imines were resolved and their absolute configurations and consequently the corresponding configurations of the enantiomers of Br-АНРС were determined by X-ray diffraction. Enantiomerically pure Schiff bases were applied as ligands to form catalysts for the enantioselective addition reaction of diethylzinc with benzaldehyde where 1-phenylpropanol was obtained with 77–91% ee.     

Molecular complexes of cobalt(II) and Zinc(II) chlorides and bromides with 1-piperidinyl dimethylcarbamodithioate (L): Crystal structures of L and [ZnLBr<Subscript>2</Subscript>]

Complexes of MX₂(M = Co, Zn; X = Cl, Br) with 1-piperidinyl dimethylcarbamodithioate (L) of composition [MLX₂] have been synthesized. The compounds have been studied by elemental analysis; X-ray diffraction; thermogravimetry; conductometry; magnetochemistry; and IR, ¹H NMR, and electronic absorption spectroscopy. The ligand molecule is coordinated to the metal atoms in a bidentate chelating mode through the thione sulfur atom and the sulfenamide nitrogen atom to form a five-membered chelate ring. The structures of L and [ZnLBr₂] have been determined by X-ray crystallography.     

Cloused cycle of production of ulltrafine polytetrafluoroethylene and new areas of use of fluoropolymer manufacture waste

The features of processes of ultrafine polytetrafluoroethylene manufacture of waste technological polytetrafluoroethylene by hydrothermal method and thermal degradation with an exhaustive fluorination in the presence of cobalt trifluoride were studied. Compositions and properties of gaseous and solid products of pyrolysis and recycling in ultrafine polytetrafluoroethylene manufacture were determined. Methods of use of ultrafine polytetrafluoroethylene, gaseous products, and spent catalyst were developed. On the basis of the experiments a closed scheme of producing ultrafine polytetrafluoroethylene was proposed in view of its application with recycling of accompanying gas fraction, and separating manufacture waste with recycling of cobalt trifluoride catalyst and using the resulting cobalt difluoride for producing composite coatings and lubricants.     

Crystal and molecular structures of pinacol ester of ferrocenyl-1,1′-diboronic acid

The molecular and crystal structure of pinacol ester of ferrocenyl-1,1′-diboronic acid was determined by X-ray crystallography. Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1289–1291, June, 2008.     

[Co(solv)<Subscript>6</Subscript>][B<Subscript>10</Subscript>H<Subscript>10</Subscript>] (solv = DMF and DMSO) for low-temperature synthesis of borides

The synthesis and structure of complexes [Co(solv)₆][B₁₀H₁₀] (solv = DMF and DMSO) have been reported. Both complexes have been prepared in a high yield by the reaction between cobalt(II) salts and closo-decaborates Cat₂[B₁₀H₁₀] in the corresponding solvent. The complexes have been characterized by elemental analysis, IR and UV spectroscopy, X-ray powder diffraction, and X-ray crystallography. The thermal properties of the compounds have been studied in the temperature range 20–600°C under argon. The conditions to form cobalt borides have been determined based on the results of thermal analysis, subsequent annealing of the complexes in various conditions, and analysis of IR spectra of the resulting thermolysis products.     

Maximum filling principle and sublattices of lanthanide atoms in crystal structures

The most important characteristics of the Voronoi-Dirichlet polyhedra (VDP) were determined for 20526 Ln atoms (Ln = La?Lu) in sublattices containing chemically identical lanthanide atoms in the crystal structures of 14659 inorganic, coordination, and organoelement compounds. The number of lanthanide VDP faces in the sublattice can vary from 4 to 36 and, irrespective of the lanthanide nature, the VDP have most often 14 faces. The Fedorov cuboctahedron is the most abundant type of VDP. In the crystal structures, Ln atoms were found to have, most often, C ₁ site symmetry (～49% of cases) and also C _s (16), C _2v (7%), or C ₂ (6%) site symmetries.     

On a way to new types of the polyfunctional and polytopic systems based on cage metal complexes: Cadmium-promoted nucleophilic substitution with low-active nucleophilic agents

The nucleophilic substitution of the reactive halogen atoms of clathrochelate precursors with soft nucleophilic agents was promoted by cadmium(II) ion using various types of cadmium-containing compounds. Cadmium(II) activates the C–Hal bond both by the coordination of halogen substituents to this ion and the formation of anionic forms of a nucleophilic agent with cadmium amides, that increase the electron density on a reactive site of this agent. The cadmium-promoted substitution reactions of the reactive chlorine ribbed substituents in the di- and hexachlorine-containing clathrochelate precursors afforded the clathrochelate ribbed-functionalized derivatives of soft nucleophiles [alcohols (including fluorinated ones) and aromatic amines (including the nucleophiles with electron-withdrawing substituents)] by efficient one-pot procedures in high yields under mild conditions with generated in situ low-basic cadmium(II) alcoholates and amides. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–Vis, ⁵⁷Fe Mössbauer, and NMR spectroscopies, and X-ray crystallography. The potential of cadmium-promoted reactions for synthesis of different types of organic and coordination compounds is discussed.     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.