The influence of Ru and Re admixtures on the size of Co particles in Co/SiO2 catalysts of the fischer-tropsch synthesis

The promotion of Co/SiO₂ catalysts with noble metals such as Ru and Re substantially decreased the mean size of Co particles and increased the fraction of superparamagnetic particles. The Langevin function was used to approximate the magnetic field dependence of magnetization. This allowed the size of Co nanoparticles to be estimated. A decrease in the temperature of the reduction of Co/SiO₂ in the presence of Ru and Re decreased the probability of the encapsulation of Co particles in carrier pores.     

Synthesis and properties of azoles and their derivatives. 36. Synthesis of 2-amino-1,3,4-oxadiazoles, 2-amino-1,3,4-thiadiazoles,and 1,2,4-triazoline-3-thiones containing indolyl radicals

On the heterocyclization of 1-(indol-3-ylcarbonyl)thiosemicarbazides, depending on the conditions of performing the reaction, either 1,2,4-triazoline-3-thiones, 2-amino-1,3,4-thiadiazoles, or 2-amino-1,3,4-oxadiazoles containing an indolyl residue in position 5 are obtained. 1,2,4-Triazoline-3-thiones and 2-amino-1,3, 4-thiadazoles have also been synthesized by the reaction of the hydrochloride of ethyl indol-3-carboximidate with thiosemicarbazides.For communication 35, see [1].Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 9, pp. 1271–1276, September, 1984.     

New organogermanium cations [RGe(OCH2CH2NME2)2]+ with intramolecular N→Ge coordination bonds

New organohalogermanes RGe(OCH₂CH₂NMe₂)₂X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N→Ge coordination bond were synthesized. According to the ¹H and ¹³C NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The structures and relative stabilities of different isomers of compounds 4–7 were studied by quantum chemical calculations at the density functional level of theory. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 892–900, May, 2007.     

Poly[μ2‐chloro‐μ2‐1,4‐oxathiane‐κ2S:S‐copper(I)]

The title complex, [CuCl(C₄H₈OS)]_n, contains infinite spiral (CuS)_n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with Cu^I, but combine into isolated centrosymmetric Cu₂Cl₂ units. The compound is non‐isomorphous with the Br‐containing analogue, which contains Cu₈S₈ rings linked by Br atoms into chains. The O atom of the 1,4‐oxathiane mol­ecule does not realize its coordination abilities in the known copper(I)–halide complexes, while in copper(II)–halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred inter­actions, viz. weak acid (Cu^I atom) with weak base (S atom) and harder acid (Cu^II atom) with harder base (O atom).     

New metal-rich mixed chalcogenides with an intergrowth structure: Ni<Subscript>5.68</Subscript>SiSe<Subscript>2</Subscript>, Ni<Subscript>5.46</Subscript>GeSe<Subscript>2</Subscript>, and Ni<Subscript>5.42</Subscript>GeTe<Subscript>2</Subscript>

New metal-rich mixed nickel-silicon and nickel-germanium chalcogenides, Ni_5.68SiSe₂, Ni_5.46GeSe₂, and Ni_5.42GeTe₂, were synthesized by high-temperature ceramic techniques. The X-ray diffraction study of single crystals grown from a molten flux revealed that the compounds are isostructural and crystallize in the tetragonal system (space group I4/mmm, Z = 2). These compounds are the first members of the family of M_7−δEX₂-type (M = Ni or Pd; E = Sn or Sb; X is chalcogen) intergrowth structures containing “light” p elements E. Resistivity measurements on pressed textured pellets showed that both selenides are anisotropic metallic conductors in the directions parallel and perpendicular to the heterometallic bond systems. The geometric criteria of stability of the intergrowth structure type under consideration are discussed. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1632–1638, September, 2007.     

Ate complexes of Ge(II) and Sn(II) with bidentate ligands [LiE(OCH2CH2NMe2)3]2 (E=Ge, Sn): synthesis and structure

The reaction of equimolar quantities of LiOCH₂CH₂NMe₂ and E¹⁴(OCH₂CH₂NMe₂)₂ (E¹⁴=Ge, Sn) in ether yielded new ate complexes [LiE¹⁴(OCH₂CH₂NMe₂)₃]₂ (E¹⁴=Ge (1), Sn (2)) with bidentate ligands. The compounds 1 and 2 are white crystalline substances which are highly soluble in THF and pyridine and very sensitive to the traces of oxygen and moisture. The structures of these compounds are studied by X-ray diffraction analysis. The ate complexes 1 and 2 are powerful nucleophiles and may be employed as ligands (neutral) in the coordination chemistry of the transition metals. The electronegative O-substituents at the divalent E¹⁴ atoms render them less oxidizable than alkyl- or aryl-substituted derivatives, and the bidentate ligands, owing to intramolecular donor-acceptor interactions, make them more thermodynamically stable compared to monodentate ligands.     

Formation of porous matrices from lactide and ε-caprolactone copolymers in supercritical carbon dioxide medium

A series of lactide and ε-caprolactone copolymers containing 4–24 mol % of ε-caprolactone with 20- to 30-kDa molecular weights are synthesized. Based on them, porous materials are produced by foaming in supercritical carbon dioxide. The pore size was shown to decrease with increasing ε-caprolactone content in copolymer, while the porosity of the entire sample was not altered. The resulting pore size also decreases if 7 wt % polyethylene glycol is added to the initial monomer mixture. The Young’s modulus of the porous samples decreases with increasing ε-caprolactone content and when polyethylene glycol is added.     

Diastereospecific ring cleavage of bornane-2,3-dione in the Bucherer-Bergs reaction

A novel regio- and diastereospecific ring cleavage of bornane-2,3-dione (camphor quinone) under Bucherer-Bergs reaction conditions has been investigated. The simplicity of this transformation provides a novel and straightforward synthetic pathway to enantiopure derivatives of cyclopentane carboxylic acid as well as functionalized hydantoins in just two steps, starting from inexpensive and easily available camphor.