Trimethylsilyl-1,3,4-oxadiazoles—new useful synthons for the synthesis of various 2,5-disubstituted-1,3,4-oxadiazoles

The reactivity of 2-aryl-5-trimethylsilyl-1,3,4-oxadiazoles toward different types of electrophiles was investigated. These silanes readily react with chlorine, bromine, aliphatic acyl chlorides, 2-nitrobenzenesulfenyl chloride, and some reactive isocyanates affording the corresponding substituted 1,3,4-oxadiazoles. The reactions with carbonyl compounds proceed only in the presence of F⁻ anions.     

Interaction of loparite concentrate with ammonium hydrodifluoride

Results obtained in a study of the interaction between the loparite concentrate and ammonium hydrodifluoride are reported. It was found that the reactions of the main components of the concentrate with NH₄HF₂ yield complex ammonium fluorometallates. It was shown that water leaching of the fluorinated product makes it possible to transfer niobium and tantalum into solution together with fluoroammonium salts of titanium and silicon and to concentrate rare-earth elements in the insoluble residue in the form of complex salts of general formula NaLnF₄.     

Magnetic and Magnetoelectric Properties of Scandoborate NdSc3(BO3)4

Physics of the Solid State - Trigonal neodymium scandoborate NdSc3(BO3)4 single crystals have been grown by the batch flux method using bismuth trimolybdate and their magnetic and magnetoelectric...     

Reversible luminescence thermochromism and phase transition in crystals of thiophenylacetylacetonatoboron difluoride

The low-temperature phase transition (−22.4 °C) is accompanied by marked change of the optical properties, as was first revealed for 3-phenylthiopentan-2,4-dionatoboron difluoride (1) in the series of β-diketonatoboron difluorides. This transition was investigated by luminescence and reflection spectroscopy, differential scanning calorimetry (DSL), X-ray analysis and atomic force microscopy methods. It was observed by the DSL method that at the room temperature the complex existed in its high-temperature modification and transformed into the stable one with ΔH=0.981 kcal/mol below −22.4 °C. The reverse transition takes place at 43.4 °C with ΔH=0.59 kcal/mol. Cooling of 1 results in a noticeable change of its morphology: the crystal cracked along the layer borders and nanometer particles were formed. Having been cooled the light-yellow crystals turned into white powder and luminescence colour changed from aquamarine to white. Heating of the cooled 1 to the 47.9 °C (the second phase transition) results in partial coincidence of the reflection and luminescence spectra, as well as those of initial single crystals that indicates the existence of size-dependent optic properties.     

Initial stages of soot formation in thermal pyrolysis of acetylene. II. A model for the incipience and growth of soot particles

A model is developed which describes simultaneously occurring processes of the initial hydrocarbon pyrolysis, nucleation, surface growth, and coagulation of soot particles. The model permits one to find the size distribution of the primary soot particles up to size 30–40 nm using a relatively small set of equations. The computed time dependence of soot particle concentration agrees satisfactorily with available experimental data. The existence of two limiting stages of the soot formation is revealed.     

Vibrational Spectroscopy Study of Fluorozirconate Glasses Containing Tin Difluoride and Gallium Trifluoride

A series of fluorozirconate glasses in ZrF₄-SnF₂-GaF₃ and ZrF₄-SnF₂-BaF₂ systems have been studied by vibrational spectroscopy. The glass net contains not only fluorozirconate polyhedra, but also fluorostannate and fluorogallate groups. When contained in amounts of more than 10 mol.% in a glass, tin difluoride is a glass-forming agent. Gallium trifluoride in the same amount or higher forms GaF₆ polyhedra.     

Relaxation Effect of Basis Orbitals on the Properties of Atomic and Molecular Hydrogen Systems

The effect of orbital relaxation on the properties of atomic and molecular hydrogen systems H, H ₂ ⁺ , H₂, H ₂ ⁻ , and H ₃ ⁺ calculated using the minimal basis set, the split valence shell basis set including the polarization function, and an extended basis set of grouped natural orbitals is considered. Inclusion of orbital relaxation in calculations results in a decreased total energy and more accurate energies of electron affinity. The strongest effect is produced on the calculated characteristics of the anions. The calculated activation energy of the radical reaction of hydrogen elimination. H₂ + H = H + H₂ depends strongly on the degree to which electron correlation is taken into account. Due to inclusion of orbital relaxation, the activation energy also approximates the experimental value, although to a lesser extent. The semiempirical PM3 method fails to adequately describe the transition state of this reaction, but this disadvantage is eliminated by using the exponent of the relaxed orbital of hydrogen.Original Russian Text Copyright © 2004 by A. I. Ermakov, A. E. Merkulov, A. A. Svechnikova, and V. V. Belousov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 979–985, November–December, 2004.