Transformations of conjugated enamines of the imidazolidine 1-oxide series in the Vilsmeier-Haack reaction

In some cases, the reactions of enaminones of the imidazolidine 1-oxide series with the Vilsmeier reagent afford electrophilic substitution products containing the dimethyl-aminomethylene group. In an acidic medium, these products undergo either hydrolytic elimination of the dimethylaminomethylene moiety or hydrolysis of the latter to form the aldehyde group. The reaction of nitroenamine, which is a derivative of imidazolidine 1-oxide, with the Vilsmeier reagent produces furoxane, viz., the nitroxyl biradical. Reduction of the latter affords the dioxime biradical. Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1170, June, 2007.     

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.     

Die Struktur des Pentaphenyldisilans

Structure of Pentaphenyldisilane For the first time Pentaphenyldisilane was prepared by Gilman and Goodman. It is produced by the reaction of Ph₃SiLi with Ph₂ClSiH. The crystal structure presents an ideally staggered conformation. The distance d(Si? Si) = 235.7 pm corresponds to a normal single bond length. This emphasizes the complete relief of the central Si? Si bond by the insertion of only one hydrogen atom.     

Darstellung SiH-haltiger Silylphosphine und Untersuchung ihrer PMR-Spektren

The preparation of SiH-containing silylphosphines from SiH-containing chlorosilanes is successful by using an excess of chlorosilans. Chemical shift data and coupling constants of the compounds H_xSi[P(C₂H₅)₂]_4?x and (CH₃)_xSi[P(C₂H₅)₂]_4?x are communicated and compared with those of H_xSiX_4?x and (CH₃)_xSiX_4?x (X = halogen or H).     

A CNDO-MO calculation of VCl4

The electronic structure of the tetrahedral molecule VCL₄ is investigated within the CNDO-MO approximations. The metal and ligand valence orbitals, 3d, 4s, 4p; and 3s, 3p; respectively, have been systematically varied in an attempt to minimize the total energy; “optimum” V 4s(χ₄ = 1.10) and 4p(d ³ p ²) orbitals have been established, but V 3d(d ⁿ ) and Cl(-δ) valence orbitals are only seen to favor lower energy for expanded orbitals. Since determining the one-electron molecular orbital level which is occupied by the vanadium lone electron is a major aspect of this investigation, all calculations have been performed in triplicate: calculations assuming the unpaired electron occupies the 3a ₁, 2 _e and 4t ₂ molecular orbital (ground state electronic configurations² A ₁,² E, and² T ₂, respectively). The Hartree-Fock equations have been solved by Roothaan's SCF method for open shells, but off-diagonal multipliers between filled and partly filled molecular orbitals of the same symmetry have been neglected. As a qualitative estimate of the error introduced by this simplification, the pertinent overlap integrals between the eigenfunctions from calculations for the three possible configurations,² A ₁,² E, and² T ₂, are investigated as functions of the component 3d(d ⁿ ) and Cl(-δ) valence orbitals. The overlap integrals from the relevant² A ₁ and² T ₂ calculations are reasonably small, but the neglect of off-diagonal multipliers in calculations on the² E state is found to be a poor approximation. An ordering of the non-filled molecular orbitals in VCl₄ of 4t ₂ < 3a ₁ < 2e < 5t ₂ seems most consistent with the numerous calculations. This suggested ground state electronic configuration of² T ₂ introduces new aspects to the consideration of a (dynamic) Jahn-Teller effect in VCl₄. Experimental data pertinent to the electronic structure of VCl₄ has been briefly summarized, but unfortunately it is inadequate to confirm or deny the present calculations.     

Hyperfine structure investigations of some odd levels of Co I by level crossing and optical methods

Using the level crossing technique the ratios and absolute values of the hyperfine structure (hfs) constants of the levelsz ⁴F_9/2 andz ⁴F_7/2 of the configuration 3d ⁷4s4p of Co I were measured:z ⁴ F _9/2: ¦A¦=(811±12)MHz; ¦B¦=(48±93) MHz;B/A=?0.06±0.11 A>0; B<0z ⁴ F _7/2: ¦A¦ = (659 ±11)MHz; ¦B¦=(33±84)MHz;B/A=?0.05±0.13 A>0; B<0. In addition the hfs constants of three other excited levels of Co I could be determined by optical methods:z ⁴ F _9/2:A=525±26 MHz;B=200 MHzy ⁴ F _9/2:A=300±30 MHz;B=?500 MHzy ⁴ G _11/2:A=315±20 MHz;B=400 MHz. The experimental results are compared with known experimental and also with theoretical values which where calculated using the parametric potential method.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

The rate of the reactions of C2O radicals with H and H2

The rate constants for the reactions C₂O + H → products (1) and C₂O + H₂ → products (2) have been determined at room temperature by means of laser-induced fluorescence detection of C₂O radicals, generated either by the KrF excimer laser photolysis Of C₃O₂, or by the reaction of C₃O₂ with O atoms. Values of k₁ = (3.7 ± 1.0) × 10^?11 cm³ s^?1 and k₂ = (7 ± 3) × 10^?13 cm³ s^?1 were obtained.     

Association of hydrofluoric acid in NaCl aqueous media under hydrothermal conditions

The apparent association constant of hydrofluoric acid Q _HF ^' in 1m NaCl aqueous media has been determined potentiometrically at pressures up to 1 kbar and temperatures up to 250°C. A concentration cell employing hydrogen electrodes was used. The association of HF increases with increasing temperature but decreases with increasing pressure.