Über Reaktionen von Nitrosophenolen, 4. Mitt.: Reaktion von Nitrosonaphtholen mit Naphtholen

Zusammenfassung Die Reaktion von 1-Nitroso-2-naphthol mit 1-und 2-Naphthol sowie die Reaktion von 2-Nitroso-1-naphthol mit 2-Naphthol in Äthanol und in Äther bei Anwesenheit von HNO₃ gibt 5H-Dibenzo[a,j]phenoxazon-(5) (I), 5H-Dibenzo[a,j]phenoxazon-(5)-14-oxid (II), 5H-Dibenzo[a,h]phenoxazon-(5) (III) sowie 5H-Dibenzo[a,h]phenoxazon-(5)-14-oxid (IV). Es wurde ein Reaktionsmechanismus vorgeschlagen und die Konstitution der hergestellten Verbindungen spektrophotometrisch und potentiometrisch bestimmt.

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The reaction of 1-nitroso-2-naphthol with 2-and 2-naphthol and the reaction of 2-nitroso-1-naphthol with 2-naphthol in ethanol or ether in the presence of nitric acid have been studied. The main reaction products isolated were the dibenzophenoxazones I–IV. The reaction mechanism for their formation is proposed.

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Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide

The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent mixture (φ_r = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN⁻ at constant 0.8 mmol dm⁻³ HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant in the presence of Cl⁻ only. The oxidation rate measured in the [FeCl]²⁺ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching the physiological pH conditions the rate constant attained the value of an order of magnitude of 10³ dm³ mol⁻¹ s⁻¹, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the presence of Cl⁻ strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm⁻³ HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity, and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step. Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10 June 2005.     

Determination of calcium in silicate rocks by potentiometric titration with ethyleneglycol-bis-(2-Aminoethylether)tetraacetic acid and a calcium-selective electrode

The method reported for the determination of calcium in silicate rocks involves titration with ethyleneglycol-bis(2-aminoethylether)tetraacetic acid (EGTA) to a potentiometric end-point. A Crytur calcium-selective electrode is used; the selectivity constants (K_ca,x) are less than 10^-3 for Mg, Ba, Sr, K and Na. The method can be used for calcium contents of 2% or higher (and exceptionally for lower contents), in the presence of up to 60% Mg, 33% AI, 17% Fe, 5% Ba, 5% Ti, and 2.5% Mn. Al, Fe and Ti are masked with sulphosalicylic acid, barium is precipitated as its sulphate, and manganese is bound as its cyanide complex. If the magnesium content is less than that of calcium, EDTA can be used as titrant, magnesium being masked with acetylacetone.     

Eliashberg theory for disordered superconductors. II. Tunneling into disordered two-dimensional Pb films

A series ofc-axis oriented YBa₂Cu₃O _x -films with different oxygen content were prepared by laser deposition. The oxygen contentx was determined by X-ray diffraction and by resonant Rutherford-back-scattering (RRBS) measurements. Thec-axis length in these films of YBa₂Cu₃O _x is about 0.5% larger compared to bulk values. We describe transport measurements in magnetic fields up to 7 Tesla between room temperature andT _c in samples with an oxygen content between the orthorhombic-to-tetragonal transition (x6.4) and full oxygenation (x7). The ratio /R _H was investigated with respect to the two-dimensional Luttinger liquid theory and the model of the two-dimensional ionic metal. We report on deviations from the expected quadratic temperature behaviour of /R _H , especially in films with high oxygen content.     

Resonances in low-energy rare-gas atom scattering

Precise values of energies and widths of low-lying resonances in some rare-gas atom systems (Ar-Ar, Ne-Kr, Ne-Xe) are reported.     

Combination of three analytical techniques for speciation of Al in environmental samples

An analytical scheme is proposed which combines three speciation techniques for determination of particular Al species in soil extracts and percolating waters. A cation-exchange fast protein liquid chromatography — inductively coupled plasma atomic emission spectrometry (FPLC-ICP-AES) procedure, a microcolumn chelating ion-exchange chromatography- atomic absorption spectrometry (MCC-ETAAS) technique and the 8-hydroxyquinoline spectrophotometric method (8HQ-spectrophotometry) were employed. The FPLC-ICP-AES procedure offers determination of Al³⁺ (retention time 4.5 min) and Al(OH)²⁺ species (retention time 4.0 min) which are separated from Al(OH)⁺ ₂ (retention time 1.5min). AlF²⁺ coelutes with Al(OH)²⁺ species, while Al(SO₄)⁺, AlF⁺ ₂ and negatively charged Al organic complexes coelute with Al(OH)⁺ ₂ species. The MCC-ETAAS technique enables determination of the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphate- and fluoro-Al complexes. Employing the 8HQ-spectrophotometry the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphato- and most of the labile organic Al species are determined. The sensitivities of these selected techniques were adequate for speciation of Al in the samples analyzed. On the basis of the specific selectivity of a particular technique various groups of Al species may be determined. Thus, the comparison of analytical data from complementary procedures provides more comprehensive information on Al species present in soil extracts and percolating waters.     

Studium des gegenseitigen Einflusses der Bindungen in Thiocyanat-Kupfer(II)-Komplexen mit Methyl- und Dimethylpyridinen mittels Infrarotspektroskopie

The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)₂ L ₂ with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)₂ L ₃ withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)₂ L ₂ complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)₂(pyridine)₂.

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Extraction of americium,lanthanides and some fission product elements by bidentate phosphonates

The extraction of Am, Eu, Ce(III), Zr(IV), and Sr from aqueous nitric acid— nitrate media by dibutyl N,N-diethylcarbamylphosphonate and dibutyl N,N-diethylcar-bamylmethylenephosphonate dissolved in carbon tetrachloride was studied. The trivalent actinide and lanthanide elements may be separated in certain aqueous phase acidity regions from Fe(III), Zr(IV), and Sr, whereas the separation of actinide elements from the lanthanide elements is poor. The extractant to metal ratio in the extracted complexes of Am, Eu, and Ce(III) is 3. The interferences in the extraction due to acidic impurities in the extracting agent are discussed.     

Correction procedure for the electron microprobe analysis of porous materials

A correction method is proposed for the quantitative determination of stoichiometric ratios in porous materials by electron microprobe analysis. Analysis of this kind of material is complicated by an imperfect surface that can only be improved to some extent. The correction is based on a linear dependence (different for each element) of the analyses on a sum of weight concentrations of oxides. With this correction it is possible to use analyses affected by the imperfection of the surface with much better confidence compared to common normalisation. An example is presented for a series of ceramic superconductors Bi_2.1(SrCa)_2.9Cu₂O₈₊.     

Ligandenfeldspektren einiger Cyanato-Kupfer(II)-Komplexe des Typs Cu(NCO)2 L 2 mit Liganden aus der Chinolin- und Isochinolingruppe Cyanato-Kupfer(II)-Komplexe mit organischen Liganden, 7. Mitt.

Zusammenfassung Die Ligandenfeldspektren der Komplexe des Typs Cu(NCO)₂ L ₂ (L=Ligand der Chinolin- bzw. Isochinolingruppe) im festen Zustand wurden aufgenommen. Das Spektrum des Komplexes Cu(NCO)₂(Chin)₂ weist eine einzige Bande auf und deutet auf eine pseudooktaedrische Struktur. Die Spektren der übrigen Komplexe enthalten hingegen neben den Hauptbanden auch Schultern bzw. ist die anwesende Bande zusammengesetzt, so daß diese Spektren mit einer planaren Struktur im Einklang sind. Die annähernden Werte für den Parameter 10Dq wurden berechnet; sie liegen im Bereich von 7,1 bis 7,8 kK.

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Ligand field spectra of some cyanato-copper(II) complexes with ligands from the quinoline- and isoquinoline group

The ligand field spectra of complexes of the type Cu(NCO)₂ L ₂ (L=ligand from the quinoline or isoquinoline group) in the solid state were recorded. Only the spectrum of Cu(NCO)₂(Quin)₂ exhibits a single band and indicates a pseudooctahedral structure, while the spectra of the remaining complexes also contain shoulders in addition to the main band, or this band is composite, thus being in accordance with a planar structure. The approximate values of the parameter 10Dq were calculated and found to be in the range of 7.1 to 7.8 kK.

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6. Mitt.:M. Quastlerová-Hvastijová, J. Kohout undJ. Gao, Z. anorg. allgem. Chem., im Druck.