Synthesis,crystal structure and stereochemical non-rigidity of (O-Sn)-bischelated bis(lactamomethyl)dichlorostannanes

Previously unknown (0-Sn)-bischelated bis(lactamomethyl)dichlorostannanes have been synthesized by a direct method from metallic tin and N-chloromethyllactams. According to X-ray structural analysis data, in the solid state in these compounds the tin atom is hexacoordinated and has an octahedral configuration with the two carbon atoms in the transposition, and both coordinating oxygen atoms and the two halogen atoms in thecis-position. A comparison to Ge-analogs indicates that the replacement of the central atom of the coordination unit MCl₂O₂C₂ has inconsistent effects on the parameters of the latter. According to¹H and¹¹⁹1 Sn NMR data, the hexacoordination of tin and the geometry of the coordination unit are also retained in solution at low temperatures. At higher temperatures a dynamic process takes place resulting in isochronisms of the protons signals of the NCH₂Sn groups. Quantum-chemical calculations of isomeric bis(lactamomethyl)dichlorostannanes by MNDO and MNDO/PM3 methods have been discussed.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp 2768–2779, November, 1996.     

Synthesis and Thermal Stability of N-(Chlorodimethylgermylmethyl)-N-methyl-O-(trimethylsilyl)salicylamide

Russian Journal of General Chemistry -     

Mössbauer and magnetic studies of La0.8Sr0.2CoO3-δ CMR perovskite

In this paper we present ⁵⁷Co emission Mössbauer and AC magnetic susceptibility studies of La_0.8Sr_0.2CoO_3-δ perovskite. The observed coexistence of paramagnetic and magnetic subspectra in the ⁵⁷Co emission Mössbauer spectra, as well as the difference of their isomer shifts support the existence of electronic phase separation in this perovskite, in good agreement with the double exchange based cluster model.     

Response of La0.8Sr0.2CoO3-δ to perturbations on the CoO3 sublattice

Emission and transmission M?ssbauer studies of La_0.8Sr_0.2CoO_3-δ perovskites doped with ∼0.02 stoichiometric units of oxygen vacancy or 2.5% iron corroborate the occurrence of electronic phase separation in these systems. The effect of the small perturbation of the CoO₃ sublattice with either iron ions or oxygen vacancies on the bulk magnetization as well as on the M?ssbauer spectra is in good agreement with the double exchange based cluster model. The magnetoresistance does not show any peak near the Curie temperature, but reaches -84% in a field of 7.5 T at T = 8 K. Below T_C ≈ 180 K the M?ssbauer spectra distinctly include the contribution from paramagnetic and ferromagnetic regions, providing direct evidence for phase separation. No contribution to the spectra from Fe⁴⁺ ions can be observed, which is an unambiguous evidence that at low concentration iron (either directly doped or formed from ⁵⁷Co by nuclear decay) is accommodated in the cobaltate lattice as Fe³⁺ ion.     

Synthesis, crystal and molecular structures, and steroechemical nonrigidity ofN-(chlorodimethylgermylmethyl)-andN-(bromodimethylgermylmethyl)-N-[(S)-1-phenylethyl]acetamides andN-(chlorodimethylgermylmethyl)-4-phenyl-2-pyrrolidone

RacemicN-(chlorodimethylgermylmethyl)-4-phenyl-2-pyrrolidone and the first optically active amide derivatives containing the asymmetrical carbon atom and the five-coordinate germanium atom,viz.,N-(chlorodimethylgermylmethyl)- andN-(bromodimethylgermyl-methyl)-N-[(S)-1-phenylethyl] acetamides, were synthesized. Their structures were established by X-ray diffraction analysis. The geometric characteristics of the trigonal-bipyramidal valence environment about the germanium atoms are compared with those of analogous enantiomeric silicon compounds and the related five-coordinate germanium compounds. The barriers to permutational isomerization of the title compounds were determined by dynamic¹H NMR spectroscopy. It was found that these barriers are higher than those of the corresponding silicon analogs. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 137–144, January, 2000.     

Quantum-Chemical Study of Electronic and Steric Structure of Vinyltetrazoles: I. 2-Substituted 5-Vinyltetrazoles

The total Mulliken charges on the carbon atoms of the vinyl group, populations of S-trans-(N¹)conformers, and internal rotation energies were calculated ab initio (HF/6-31G**, MP2/6-31G**, and MP2/6-31G**//AM1) for a series of 2R-5-vinyltetrazoles (R = CH₃, C₂H₅, i-C₃H₇, t-C₄H₉, C₆H₅). The calculation results were compared to the available experimental data.     

Three-dimensional flow in axial flow fans of non-free vortex design

Three-dimensional laser Doppler anemometer (LDA) measurements were carried out downstream of isolated axial fan rotors of non-free vortex design in order to investigate the role of radial velocity components in design. The structure of secondary flows due to non-free vortex operation was studied in detail. It is pointed out that the tangential gradient of radial velocity at midspan is nearly in direct proportion with the spanwise gradient of ideal total head rise prescribed in design. Design criteria have been established for the neglect of torsion of stream surface segments inside the blading. A linear relationship was proposed in order to estimate the pitch-averaged radial velocities at the rotor exit. Using this relationship, a proposal has been put forward for taking the radial velocity components into account in non-free vortex design with the assumption of conical stream surfaces through the blading.