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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1431-1435 
    ISSN: 0044-2313
    Keywords: Titanium(IV) Chelates ; Tridentate Diacidic Ligands ; Mass Spectra, Charge Transfer Band, Structure of Bis[2,6-diphenacylpyridinato(2-)]titanium(IV) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Titanium(IV) Complexes with Tridentate Diacidic Ligands. Crystal Structure of Bis[2,6-diphenacylpyridinato(2-)]titanium(IV)The titanium(IV) chelates with 2,2′-dihydroxy-azobenzene, salicylaldehyde-2-hydroxyanil, 2-(2′-hydroxyphenyl)-8-quinolinol, 2,6-diphenacylpyridine as well as with aroylhydrazones of salicylaldehyde, benzoylacetone and thenoyltrifluoroacetone were synthesized by ligand exchange reactions of titanium(IV)-isopropoxide. The compounds are red or black in colour and were identified by distinct molecular peaks in the mass spectra. The crystal and molecular structure was determined for bis[2,6-diphenacylpyridinato(2-)] titanium(IV). Crystallographic data see “Inhaltsübersicht”.
    Notes: Durch Ligandenaustauschreaktion von Titan(IV)-isopropoxid mit 2,2′-Dihydroxyazobenzen, Salicylaldehyd-2-hydroxyanil, 2-(2′-Hydroxyphenyl)-chinolin-8-ol, 2,6-Diphenacylpyridin sowie Aroylhydrazonen-von Salicylaldehyd, Benzoylaceton und Thenoyltrifluoraceton wurden die Titan(IV)-Chelate dieser Liganden dargestellt. Die roten bis schwarzen Verbindungen zeigen im Massenspektrum das erwartete Molekülion. Für Bis[2,6-diphenacylpyridinato(2-)]-titan(IV) wurde die Kristall- und Molekülstruktur bestimmt: Gitterabmessungen bei 293 K, a = 1 448,6(7) pm, b = 776,1(5) pm, c = 1 520,7(5) pm, β = 104,65(3)°, Raumgruppe Pc, Z = 2, 3 755 unabhängige Reflexe, R = 5,5%.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0044-2313
    Keywords: Supersilylzinc ; Supersilylcadmium ; Supersilylmercury ; X-ray structure analyses ; Supersilyl radical, Supersilanidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Disupersilylmetals (tBu3Si)2M and Supersilylmetal Halides tBu3SiMX with M = Zn, Cd, Hg: Syntheses, Properties, StructuresDisupersilylmetals (tBu3Si)2Zn (colorless), (tBu3Si)2Cd (light yellow), (tBu3Si)2Hg (light yellow), and supersilylmetal halides tBu3SiZnCl(THF) (colorless), tBu3SiCdI (colorless), tBu3SiHgCl (colorless) are obtained in THF by the action of tBu3SiNa on ZnCl2, CdI2, HgCl2 in the molar ratio 2:1 and 1 :1, respectively. THF can be exchanged by TMEDA under formation of tBu3SiZnCl(TMEDA), and (tBu3Si)2Zn transforms by the action of BiCl3 or BBr3 into tBu3SiZnCl (colorless) and tBu3SiZnBr (colorless), respectively. As to X-ray crystal structure analyses, the compounds (tBu3Si)2M are monomeric with a linear SiMSi framework, whereas tBu3SiZnBr and tBu3SiHgCl are tetrameric, the former with a regular, the latter with a pronounced irregular cubic M4X4 framework. The compounds are thermal stable up to 200°C (exception (tBu3Si)2Cd), photolabile, and comparatively inert for water and oxygen. The disupersilylmetals work as sources of supersilyl radicals tBu3Si (on irradiation) and as mild supersilanidation agents (e.g. (tBu3Si)2Zn/BBr3 → tBu3SiZnBr/tBu3SiBBr2), the supersilylmetal halides as Lewis acids (formation of tBu3SiMX · donor) and electrophiles (e.g. tBu3SiHgCl/RLi → tBu3SiHgR/LiCl).
    Notes: Disupersilylmetalle (tBu3Si)2Zn (farblos), (tBu3Si)2Cd (blaßgelb), (tBu3Si)2Hg (blaßgelb) und Supersilylmetallhalogenide tBu3SiZnCl(THF) (farblos), tBu3SiCdI (farblos), tBu3SiHgCl (farblos) bilden sich in THF durch Einwirkung von tBu3SiNa auf ZnCl2, CdI2, HgCl2 im Molverhältnis 2 : 1 bzw. 1 : 1. THF läßt sich durch TMEDA unter Bildung von tBu3SiZnCl(TMEDA) (farblos) ersetzen, (tBu3Si)2Zn durch Einwirkung von BiCl3 oder BBr3 in tBu3SiZnCl (farblos) oder tBu3SiZnBr (farblos) umwandeln. Gemäß Röntgenstrukturanalysen sind die Verbindungen (tBu3Si)2M monomer mit linearen SiMSi-Gerüsten, wogegen tBu3SiZnBr und tBu3SiHgCl tetramer sind, und zwar in ersterem Falle mit regulärem, in letzterem mit ausgeprägt irregulärem kubischem M4X4-Gerüst. Die Verbindungen sind bis 200°C thermostabil (Ausnahme (tBu3Si)2Cd), photolabil und vergleichsweise stabil gegen Wasser und Sauerstoff. Die Disupersilylmetalle wirken als Quellen für Supersilylradikale tBu3Si (bei Bestrahlung) sowie als milde Supersilanidierungsmittel (z. B. (tBu3Si)2Zn/BBr3 → tBu3SiZnBr/tBu3SiBBr2), die Supersilylmetallhalogenide als Lewis-Säuren (Bildung von tBu3SiMX · Donor) und Elektrophile (z. B. tBu3SiHgCl/RLi → tBu3SiHgR/LiCl).
    Additional Material: 6 Ill.
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