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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 24 (1985), S. 742-757 
    ISSN: 0570-0833
    Keywords: Polysulfides ; Transition metals ; Chelates ; Sulfides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been long known that certain transition metal sulfides dissolve in aqueous ammonium polysulfide. Although it was assumed that they thereby formed metal polysulfides, attention was first paid to such compounds only a few years ago. In recent years a host of new complexes with polysulfido chelate ligands have been isolated and characterized. The complexes are of interest not only regarding their structure and reactivity but also in view of their potential uses; they can be used for the directed preparation of sulfur rings of a given size, and there are indications that they will find applications in catalysis.
    Additional Material: 26 Ill.
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  • 12
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on Systems of Salts and Mixed Solvents. XXXIV. 27Al and 1H N.M.R. Spectroscopic Investigations of AlCl3-Water-N,N-Dimethylformamide SolutionsAl3+ ions exist in aqueous solutions as well as in DMF solutions in a sixfold coordination; the coordination of DMF exclusively occurs via the oxygen atom. Because of the small shift difference between the pure aqueous and the pure DMF solution at the 27Al n.m.r. spectra no separated signals were found corresponding to the species with mixed coordination. From the changes of the Al chemical shifts and of the linewidths in dependence of the solvent composition a selective solvation process is suggested. At the 1H n.m.r. spectra for the formyl and methyl protons of DMF separated signals appear for the molecules of the first coordination sphere and of the bulk, respectively. From this the number of directly coordinated DMF molecules can be determined. Up to a DMF content of about x = 0.45 DMF is preferentially coordinated, after that a change of selectivity takes place and accordingly water is preferred at the first coordination sphere.
    Notes: Al3+-Ionen werden sowohl in wäßrigen als auch in DMF-Lösungen sechsfach koordiniert, die Koordination des DMF erfolgt über Sauerstoff. Wegen der geringen Verschiebungsdifferenz zwischen der reinen wäßrigen und der reinen DMF-Lösung treten in den 27Al-NMR-Spektren mit gemischtem Lösungsmittel keine getrennten Signale für gemischt-koordinierte Spezies auf. Aus den Änderungen der Al-chemischen Verschiebung und der Halbwertsbreite der Signale in Abhängigkeit von der Lösungsmittelzusammensetzung werden Hinweise auf eine selektive Solvatation erhalten. In den 1H-NMR-Spektren erscheinen für die Formyl- und Methylprotonen des DMF getrennte Signale für die Moleküle in der ersten Koordinationssphäre und die des restlichen Lösungsmittels. Daraus läßt sich die Anzahl der direkt koordinierten DMF-Moleküle ermitteln. Bis zu einem DMF-Gehalt von x s≈ 0,45 wird bevorzugt DMF koordiniert, danach tritt ein Selektivitätswechsel auf, so daß bevorzugt Wasser koordiniert wird.
    Additional Material: 5 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 544 (1987), S. 225-231 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N.M.R. Investigations of Fluorodiazadiphosphetidines and Fluoro-λ5-monophosphazenesThe 19F and 31P n.m.r. data of 37 fluorodiazadiphosphetidines [RR′PF—NC6H4X]2, and 62 fluoro-λ5-monophosphazenes, RR′PF=NC6H4X, are submitted. In the case of tetrafluorodiazadiphosphetidines, [RPF2—NC6H4X]2, an intramolecular exchange of the fluorine atoms at phosphorus has to be concluded from the n.m.r. data. The influence of the substituents R and X on the n.m.r. parameters is discussed using simple models of molecular structure.
    Notes: Es werden die 19F- und 31P-NMR-Daten von 37 Fluorodiazadiphosphetidinen, [RR′PF—NC6H4X]2, und 62 Fluoro-λ5-monophosphazenen, RR′PF=NC6H4X, mitgeteilt. Aus ihnen muß für die Tetrafluorodiazadiphosphetidine, [RPF2—NC6H4X]2, auf einen intramolekularen Positionswechsel der Fluoratome am Phosphor geschlossen werden. Der Einfluß der Substituenten R und X auf die NMR-Parameter wird anhand einfacher Modelle der Molekülstruktur diskutiert.
    Additional Material: 1 Ill.
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  • 14
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on Systems of Salts and Mixed Solvents. XXXVI. 1H and 27Al N.M.R. Spectroscopic Investigations of the Solvation Behaviour in Concentrated AlCl3-Water-Alcohol Solutions1H. n.m.r. spectroscopic investigations in dependence on the solvent composition and the salt concentration are useful for the characterization of solvation processes in concentrated solutions of AlCl3-water-methanol, -ethanol, -ethylene glycol, and -diethylene glycol. In these systems water is preferentially coordinated at the first coordination sphere of the Al3+ ion within the whole region of the solvent composition.The nature of the solvation species has been investigated using 27Al n.m.r. spectroscopy. In order to reduce the „solid-type“ interactions in the concentrated solutions the Magic Angle Spinning method (MAS) was used. Particularly water-poor and water-free solutions produce structured 27Al-Mas-signals. For the system AlCl3-water-ethanol an identification of solvation species is given.
    Notes: Durch 1H-NMR-Untersuchungen in Abhängigkeit von der Lösungsmittel-zusammensetzung und der Salzkonzentration werden Solvatationsprozesse in konzentrierten Lösungen von AlCl3-Wasser-Methanol, -Ethanol, -Ethylenglycol und -Diethylenglycol näher charakterisiert. Es wird jeweils eine bevorzugte Solvatation des Al3+-Ions durch Wasser über den gesamten Zusammensetzungsbereich der Lösungsmittel festgestellt.27Al-NMR-Untersuchungen dienen zur Identifizierung von Solvatationsspezies. Zur Reduzierung der festkörperähnlichen Wechselwirkungen in den konzentrierten Elektrolytlösungen wurde die Methode der schnellen Probenrotation um den „magischen“ Winkel (MAS) eingesetzt. Insbesondere wasserarme und wasserfreie Lösungen der Systeme zeigen strukturierte 27Al-MAS-Signale. Im System AlCl3-Wasser-Ethanol wird eine Identifizierung von Solvatationsspezies vorgenommen.
    Additional Material: 8 Ill.
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  • 15
    ISSN: 0749-1581
    Keywords: 27Al NMR spectroscopy ; MAS technique ; Concentrated electrolyte solutions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conventional liquid-state 27Al NMR spectra of concentrated solutions of the AlCl3-water-N,N-dimethyl-N-Dimethylformamide formamide system contain comparatively broad non-structured lines. Application of MAS leads to a reduction in the line width and a structuring of the spectra. This allowed the experimental determination of the chemical shifts of [Al(H2O)6-x(DMF)x]3+ (x = 0-6) mixed-ligand complexes. The investigations demonstrate an example of the applicability to liquids of the NMR MAS technique, which was originally developed for solids. They underline the existence, in a reduced form, of ‘solid-type’ interactions within the investigated solutions.
    Additional Material: 2 Ill.
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