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  • Gallium  (2)
  • (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, X-ray crystal structure  (1)
  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1449-1456 
    ISSN: 0009-2940
    Schlagwort(e): [Tris(trimethylsilyl)cyclopentadienyl]lithium complexes ; [Bis(trimethylsilyl)cyclopentadienyl]lithium complexes ; (Di-tert-butylcyclopentadienyl)lithium complexes ; Pentagonal-pyramidal cyclopentadienyllithium complexes ; (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, X-ray crystal structure ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis and Structure of Lithium Complexes with Pentahapto-Bonded, Substituted Cyclopentadienyl LigandsThe reaction of [tris(trimethylsilyl)cyclopentadienyl]lithium, [bis(trimethylsilyl)cyclopentadienyl]lithium, and (di-tert-butylcyclopentadienyl)lithium with Lewis bases (ethers, amines, thioethers) leads to the crystalline, air-and moisture-sensitive adducts 1a-k, 2a-c, and 3a-c, which are monomeric in the solid state, in solution, and in the gas phase. The cyclopentadienyl ligand is pentahapto-bonded to the lithium atom. In the case of [tris(trimethylsilyl)cyclopentadienyl]lithium the use of monodentate ethers results in the isolation of complexes (1a-d, 1h, 1i) with an unusual coordination of the lithium ion. Thus, the crystal structure analysis of (tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]-lithium, [(Me3Si)3C5H2]Li · THF (1b), shows a nearly linear arrangement between the oxygen atom of the THF molecule, the lithium atom, and the ring centroid of the cyclopentadienyl ligand (Li—O = 187 pm; Li—Cp centroid = 180 pm).
    Notizen: Die Umsetzung von [Tris(trimethylsilyl)cyclopentadienyl]lithium, [Bis(trimethylsilyl)cyclopentadienyl]lithium und (Di-tert-butylcyclopentadienyl)lithium mit Lewis-Basen (Ether, Amine, Thioether) führt zu kristallinen, sehr luft- und feuchtigkeitsempfindlichen Addukten 1a-k, 2a-c und 3a-c, die im Festkörper, in Lösung und in der Gasphase monomer vorliegen. Der Cyclopentadienylligand ist jeweils pentahapto an das Lithiumatom gebunden. Im Fall von [Tris(trimethylsilyl)cyclopentadienyl]lithium gelingt bei Verwendung von einzähnigen Ethern die Isolierung von Komplexen (1a-d, 1h, 1i) mit ungewöhnlicher Koordination des Lithum-Ions. So zeigt die Röntgenstrukturanalyse von (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, [(Me3Si)3C5H2]Li·THF (1b), eine nahezu lineare Anordnung zwischen dem Sauerstoffatom aus dem THF-Molekül, dem Lithiumatom und dem Ringzentrum des Cyclopentadienylliganden (Li—O = 187 pm; Li—Cp-Zentrum = 180 pm).
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    ISSN: 1434-1948
    Schlagwort(e): Aluminium ; Gallium ; Diazo compounds ; Dimerization ; Coordination modes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Lithium trimethylsilyldiazomethanide Li(SiMe3)CN2 reacted with the dialkylaluminium or -gallium halides R2AlCl and R2GaBr [R = CH(SiMe3)2] by the elimination of lithium halide and the formation of the corresponding aluminium or gallium diazo compounds. As shown by a crystal structure determination, the gallium derivative 1 adopts the nitrile imine structure, in which the gallium atom is coordinated by the terminal nitrogen atom of the diazo group. The N-N-C-Si moiety is almost ideally linear with N-N and C-N bond lengths of 125.5 and 115.9 pm on average. In contrast, the diazomethane structure was formed with dialkylaluminium chloride, and the aluminium atom in 2 is attached to the carbon atom of diazomethane. The almost linear N-N-C group (174.1°) has N-N and N-C distances of 120.0 and 126.4 pm, respectively, inverse to that of the gallium derivative. The bonding situations can best be described by the resonance structures R-C≡N+-N--GaR2 for 1 and R2Al-(R)C=N+=N- for 2. The nitrile imine isomer of the aluminium compound could be detected by NMR spectroscopy as a by-product. Both compounds gave dimers in the solid state, a Ga2N2 four-membered heterocycle was formed of 1, while an eight-membered Al2C2N4 heterocycle resulted with 2.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1661-1665 
    ISSN: 1434-1948
    Schlagwort(e): Gallium ; Low-valent compounds ; Macrocycles ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) 1 reacts with dicarboxylic acids like 1,4-benzenedi(methylcarboxylic) acid, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, and 1,4-butanedicarboxylic acid (adipinic acid) by the release of two equivalents of bis(trimethylsilyl)methane and the retention of the Ga-Ga bond. Products are formed, in which the very short Ga-Ga bonds (237.7 pm on average) are bridged by two carboxylato groups. Two of these moieties are connected in each compound by two spacers (dimethylbenzene, cyclohexane, hexane, or butane) to form macrocyclic compounds with up to 22 atoms in the resultant heteroatomic rings. The dimeric form is also observed in solution. For comparison, the synthesis and structure of the product of the reaction of 1 with 1-adamantanecarboxylic acid is included, which also has the Ga-Ga bond (239.1 pm) bridged by two carboxylato groups.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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