Alkoxylierung von bis(trimethylsilyl)-aminofluorsilanen,sowie siloxanbildung unter äthereliminierung

The reaction of bis(trimethylsilyl)aminofluorsilanes, (Me₃Si)₂NSiF₂R (R = CH₃ or F), with sodium alcoholates or sodium phenylate yields under elimination of NaF alkoxy- and aryloxy-aminofluorosilanes of the composition (Me₃Si)₂NSiF(R)OR′(R′ = CH₃, C₂H₅, C₃H₇, C₆H₅). A disiloxane is formed by thermal elimination of diethyl ether from bis(trimethylsilyl)aminomethylfluoroethoxysilane. The IR, mass, ¹H and ¹⁹F NMR spectra of the above-mentioned compounds are reported. ab]Die Reaktion von Bis(trimethylsilyl)-aminofluorsilanen des Typs (Me₃Si)₂NSiF₂R (R = F, CH₃) mit Natriumalkoholaten und Natriumphenolat führt unter NaF-Abspaltung zu Alkyl- und Aryloxyaminofluorsilanen der Zusammensetzung: (Me₃Si)₂NSiF(R)OR′ (R′ = CH₃, C₂H₇, C₆H₅, C₆H₅). Ein Disiloxan könnte durch die thermische Eliminierung von Diäthyläther aus Bis(trimethylsilyl)aminomethyl-fluor-äthoxy-silylarnin erhalten werden.Die IR-, Massen-, ¹H- und ¹⁹F-NMR-Spektren der dargestellten Verbindungen werden mitgeteilt.     

Eine neue Methode zur Bestimmung des spezifischen Kaliumpermanganatverbrauches von Humins?uren

Zusammenfassung Es wird eine indirekte Methode zur Bestimmung des spezifischen Kaliumpermanganatverbrauches von Huminsäuren beschrieben. Die Huminsäuren werden mit einer 0,01 m Blei(II)-nitratlösung gefällt und der gebildete Pb-Huminsäure-Niederschlag ausgewogen. Aus dem PbGehalt und dem Kaliumpermanganatverbrauch des Pb-HuminsäureKomplexes ergibt sich der Kaliumpermanganatverbrauch pro Milligramm Huminsäure. Im Gegensatz zu Eisen(III)-chlorid verändert Blei(II)nitrat die Oxydierbarkeit der Huminsäuren nicht, so daß indirekt und direkt bestimmter spezifischer Kaliumpermanganatverbrauch übereinstimmen.Es wurden die spezifischen Kaliumpermanganatverbrauchswerte von zwei Huminsäuren bekannter Oxydierbarkeit (Fluka-Humussäure und Moorwasser-Huminsäure) und von Huminsäuren aus 3 natürlichen Wässern bestimmt. Die Fehlerbereiche der Mittelwerte betragen bei den Modellsubstanzen (je 15 Analysenwerte) ±4% (Huminsäure Fluka) bzw. ±3% (Moorwasser-Huminsäure) und bei den praktischen Analysen ±4% ±11% bzw. ±7% des jeweiligen Mittelwertes.

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Summary An indirect method for the determination of the specific permanganate consumption of humic acids is described. The humic acids are precipitated by 0,01 M lead(II)nitrate and the precipitate of lead-humic acid is weighed. The permanganate consumption per mg humic acid results from the lead-content and the permanganate consumption of the lead-humic acid complex. As opposed to ferric chloride lead(II) nitrate does not change the oxidizability of humic acids; hence, indirectly and directly determined permanganate consumption equal each other. — The values of the specific permanganate consumption of two humic acids of known oxidizability and of three samples of humic acids isolated from natural water-sources are determined. The limit of error of the mean values is between ±3% and ±11%.

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Wir danken Frl. Roswitha Raspe und Frau Helga Boje für fleißige technische Mitarbeit.     

Selective oxidation and reduction of trinuclear titanium(II) hexaazatrinaphthylene complexes-synthesis, structure, and electrochemical investigations

Titanocene complexes with chelating N-heterocyclic ligand bridges react with ferrocenium salts as selective oxidants to afford air-stable cationic complexes and allow the preparation of exceptional mixed valence hexaazatrinaphthylene complexes [(Cp2Ti)3(mu3-HATNMe6)]n+ (1n+) (n=1, 2, 3, 4). Cyclic voltammograms (CV) and differential pulse voltammograms (DPV) show that nine oxidation states of 1 are generated without decomposition. Comproportionation constants Kc have been calculated in order to determine the extent of electronic communication between the titanium centers. The Kc values of the mixed valence states are indicative of uncoupled (14+), moderately coupled (15+), and strongly coupled (1-, 1+, and 12+) systems. Small but significant structural changes occurring upon oxidation of neutral 1 are observed by X-ray structural analysis on 1+-14+. Anion-pi interactions between the electron-deficient central ring of the HATNMe6 moiety and PF6- and BF4- counterions, respectively, are found for 12+, 13+, and 14+. The short cation-anion contacts cause interesting molecular allignments in terms of molecular architecture. For 12+ the assembly of an one-dimensional (1D) polymer is observed. Electrochemical investigations on the mononuclear cationic titanocene complexes [(Cp2Ti)(L)]+ (L=2,2'-biquinoline (2+), 4,4'-dimethyl-2,2'-biquinoline (3+), and 5,8'-dimethyl-2,3'-biquinoxaline (4+)) showed similar oxidation and reduction characteristics among each other. Conversion to monoanionic, neutral, and dicationic states is enabled. As found for the trinuclear compounds 1n+, the molecular structures of 2+-4+ reveal significant differences compared to their neutral parents.     

Trace analysis of bromate and bromide with ion chromatography on coated reversed phase materials

 The ion-chromatographic method for trace analysis of bromate and bromide presented in this paper is based on coating of reversed phase (RP) material with an ionogenic agent, tetrakisdecylammonium bromide, to obtain a pseudo ion-exchange column. The analysis is carried out with usual HPLC pump and UV-detection near 200 nm. Some commercially available RP materials were tested for the coating procedure. The differences between the reversed phases are not significant. All HETP values are calculated between 0.02 and 0.14 mm. The calibration, the sensitivity of the method and the long-time stability of the coated column were tested with one selected RP material. It is shown that the simultaneous trace analysis of bromate and bromide in surface and drinking waters with chloride concentrations up to 50 mg/L is possible without any clean-up on Ag precolumns. A comparison of performance data with a determination method for bromate and bromide employing a commercially available equipment demonstrates the efficiency of the new technique. Received: 23 February 1996/Received: 10 May 1996/Accepted: 14 May 1996     

Properties of liquid-crystalline copper(II) complexes and their binary mixtures

Abstract

Eight new copper compounds with mesogenic properties from the series of the bis{1-[4-trans-(4-alkylcyclohexy1)phenyl]-alkylpropane-1,3-dionato} copper(II) complexes have been prepared. The thermal behaviour of these compounds was investigated by means of polarizing microscopy and differential scanning calorimetry (D.S.C.) measurements. The mesophase, which could be found in most of them, is of the monotropic nematic type. This has been confirmed by miscibility experiments. The physical data of a binary mixture with an enantiotropic mesophase are also presented. In addition the crystal structures of two of the compounds are reported.     

Studies on azaspiracid biotoxins. I. Ultrafast high-resolution liquid chromatography/mass spectrometry separations using monolithic columns

In this study, the performance of monolithic columns was evaluated for ultrafast liquid chromatography/mass spectrometry (LC/MS) analyses and for high-resolution separations of several azaspiracid biotoxin analogs. Because of their high permeability, monolithic columns offer a number of advantages over conventional packed columns; viz., very low backpressures and relatively flat van Deemter curves at high flow rates. That is, very high flow rates can be used for ultrafast analyses or, by using longer than normal columns, high-resolution separations are possible. In a series of experiments, we varied the mobile phase flow rates between 1 and 8 mL/min, and studied their impact on chromatographic parameters such as retention time, resolution, number of plates and pressure. The chromatographic run times could be reduced to ca. 30 s without a significant change in the separation efficiency. A signal intensity comparison revealed interesting differences between atmospheric-pressure chemical ionization (APCI) and electrospray ionization (ESI) in their flow-rate dependency. An explanation with respect to the behavior as of a mass-flow or a concentration-dependent device is given in the paper. Additionally, the column length was varied between 10 and 70 cm. As a result, the number of theoretical plates increased substantially. In the example shown in the report, an increase from 13 000 plates for a 10-cm column to 80 000 for a 70-cm column is demonstrated. In addition, the potential of the monolithic columns for high-resolution LC/MS separations is shown for a complex biotoxin mixture, which was separated on a 40-cm-long column.     

Vibrational spectra of chloroform, freon-11 and selected isotopomers in the terahertz region

The fundamental bands of the CCl₃ asymmetric deformation modes of selected isotopomers of chloroform (CHCl₃) and freon-11 (CFCl₃) have been measured in a static cell at ambient temperature using a laser-based source of tunable radiation in the terahertz region of the electromagnetic spectrum. The analysis of the rotational contours of the bands enabled the derivation of the fundamental frequencies with an accuracy of better than 3 GHz.