Ternäre Lithium-Selten-Erd-Nitrate mit einsamen Nitrationen: Li3[M(NO3)5](NO3) (M = Gd?Lu,Y). Die Kristallstruktur von Li3Er(NO3)6

Ternary Lithium Rare Earth Nitrates with Lonesome Nitrate Ions: Li₃[M(NO₃)₅](NO₃) (M = Gd? Lu, Y). The Crystal Structure of Li₃Er(NO₃)₆ Single crystals of the ternary nitrate Li₃Er(NO₃)₆ are obtained from a solution of “Er(NO₃)₃” in the melt of LiNO₃. In Li₃Er(NO₃)₆ (monoclinic, P2₁/n, Z = 4; a = 776.0(1); b = 748.86(8); c = 2 396(1) pm; β = 90.76(3)°; R1 = 0.0490; wR2 = 0.0792), Er³⁺ is surrounded by five bidentate nitrate ligands yielding the anionic units [Er(NO₃)₅]^2?. These are arranged in the direction of the 2₁ screw axis. Two lonesome NO₃^? ions are in the middle of such a “helix” and are connected by Li⁺ with the anions [Er(NO₃)₅]^2?. The helices are moved against each other by about half of the lattice constant a and are connected by further Li⁺ ions.     

1-氟代糖在化学-酶法合成糖类中的应用

化学-酶法合成糖类具有立体选择性和区域选择性, 逐渐成为糖类合成的主流. 1-氟代糖作为糖基供体应用于化学-酶法合成反应, 显示出越来越重要的作用, 综述了1-氟代糖在糖基转移酶和糖苷酶催化的糖类合成中的应用.     

On the difference between hydrogen fluoride and hydrogen chloride crystals

The geometrical and energetical parameters of hydrogen fluoride and hydrogen chloride crystals are calculated using the periodic Hartree–Fock method with 6-31G and 6-31G(d,p) basis sets. The comparison of the stabilisation energies reveals that HCl crystals are about 75% less stable than HF crystals. The activation energy for collective proton movements are computed and discussed in view of data of isolated infinite chains. The barriers of 13.1 and 40.0 kcal mol⁻¹ at 6-31G(d,p) level are found for HF and HCl crystals.     

S1←S0 Vibronic spectra and the structure of acetyl fluoride-h3 and acetyl fluoride-d3 molecules

UV absorption spectra of acetyl fluoride-h₃ and -d₃ (CH₃COF and CD₃COF) molecules in the region of S₁S₀ electronic transitions are investigated. The origins (0⁰ ₀ or 14^0± ₀) of these transitions are observed at 39912 and 39904 cm^–1, respectively, and some of the fundamental frequencies of these molecules in the s₀ and S₁ states are determined. In particular, the systems of torsion and inversion (out-of-plane C=O vibrations) energy levels are studied. The geometric parameters of an acetyl fluoride-h₃ molecule in the S₁ state are estimated by the theoretical simulation of the rotational contours of the 0⁰ ₀ (14^0± ₀) band. These data are used to evaluate the potential barriers to internal rotation in the S₀ and S₁ states, which were found to be 360 and 560 cm^–1 for acetyl fluoride-h₃ and 380 and 770 cm^–1 for acetyl fluoride-d₃, respectively, as well as the potential barriers to inversion in the S₁ states, which were found to be 2090 and 2370 cm^–1 for acetyl fluoride-h₃ and acetyl fluoride-d₃, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1957–1964, November, 1994.In conclusion, the authors would like to acknowledge T. S. Kuznetsova for the synthesis and purification of the AF samples.The research presented here was supported in part by the International Science Foundation under grant No. MJ 1000.     

Ion Transfer in CdF<Subscript>2</Subscript>-based Iso- and Polyvalent Solid Solutions

The ionic conductivity of solid solution Cd_0.77Sr_0.23F₂ is 1.6 × 10⁻⁴ S/cm at 500 K. The conduction mechanism changes from a vacancy mechanism to an interstitial one at 523–553 K. In solid solutions Cd_0.9R_0.1F_2.1 (R = La-Lu, Y), the activation enthalpy of conduction decreases from 0.9 to 0.8 eV with decreasing ionic radius of R³⁺, raising the 500-K conductivity from 6 ×10⁻⁶ S/cm for La³⁺to 6 × 10⁻⁵ S/cm for Lu³⁺. For crystalline Cd_0.95In_0.05F_2.05, ionic and electronic conductivities at 313 K equal 5 × 10⁻⁴ and 5 − 10⁻⁶ S/cm.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 627–632.Original Russian Text Copyright © 2005 by Sorokin, Buchinskaya, Sul’yanova, Sobolev.     

Direct anodic oxidation ofp-methoxytoluene in methanol. The effect of electrolysis conditions

The effect of anions of the supporting electrolyte (F^–, dialkylphosphate, TsO^–, and BF ₄ ^– and other electrolysis conditions (anode material, temperature, substrate concentration) on the selectivity of the direct anodic oxidation ofp-methoxytoluene in methanol into 4-methoxybenzaldehyde dimethylacetal was studied. The highest selectivity was obtained in the presence of fluoride anion.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 524–527, March, 1995.This work was financially supported by the Ministry of Science, High School and Technical Policy of the Russian Federation within the scope of the State scientific-technical program Ecologically harmless processes of chemistry and chemical technology (project No. 1.140 Low-tonnage chemical products) and by the International Science Foundation (Grant Ch-2-1246-0923).     

THE ADSORPTION OF OXYGEN OVER ThO_2-BaF_2 CATALYST

IntroductionInthcsclcctivcoxidationofalkanes.suchas'theoxidativccouplingofmcthanc(0CM)andthcoxidativcdch}'drogenationofcthanc(0DE)t0prcparccth}'lene.bothoxidcionsofthelatticeandtheox}'genspeciesovercataIystsuffocepla}'animportantrole.Althoughcxtcnsivcinvcstigationshavcbeengivcntothecharactcrizationofox}'gcnspccicsandthcreactionofox}'gcnspecicsx`ithalkanes,itisstilldifficulttosayt`hichoncsofox}'gcnspcciesarcthcactivcspecicsinthcactivation0falkancs.bccauscthenaturcofcatal}'stsandthecxperimcntc…     

Preparation and properties of rare-earth containing oxide fluoride glasses

The preparation of the rare earth containing oxide fluoride glasses LnF₃ (Ln; Y through Lu)-BaF₂-AlF₃-GeO₂ in which the nominal content of LnF₃ reached 60 mol% in maximum and their basic properties such as density, refractive index and glass transition temperature were investigated and summarized in detail. Especially, in order to discuss the local structure around the rare earth ion in the glass, the Judd-Ofelt analysis (discussion with Ω parameters) of the HoF₃-BaF₂-AlF₃-GeO₂ glasses was carried out. The unique fluorescent behavior and the magnetic properties of LnF₃-BaF₂-AlF₃-GeO₂ glasses (Ln = Tb and/or Sm) were also studied.     

Development of direct fluorination technology for application to materials for lithium battery

Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride.