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  • 1
    ISSN: 0044-2313
    Keywords: Zirconium ; Lithium ; Hydroxoligands ; Oxoligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Unusual Trimeric Bimetallic Li—Zr Complex with the Backbone [Zr3(μ2-OH)3(μ3-O)Li5] by Reaction of Zirconiumorgano and Hydrido Complexes with WaterThe reaction of compounds of the type [(LZr)(LiH)(L′)]n and [(LZr)(LiH)(L′)(alkyne)]n (L: 2,2′-Biphenolato-dianion, L′: thf, Bu3P, alkyne: Ph—C≡C—SiMe3, CH≡CH) with water at 0°C in a thf solution results in the formation of th trimeric bimetallic complex 8 [(L2Zr)3(μ2-OH)3(μ3-O)Li5(thf)8(H2O)5] in 50% yield. The X-ray analysis of 8 shows that a planar six-membered ring Zr3(μ2-OH)3 is formed. In the middle of this ring is a dianionic oxygen atom placed, coordinating to the three L2Zr centres in a planar μ3-coordination (bond angles 120,05μ). Five lithium ions stabilize the anionic backbone by bridging the biphenolato chelate ligands, which form seven-membered chelate rings with the atoms.1H-, 13C-, and 7Li-NMR spectra exhibit that the solid state structure remains unchanged in solution (thf).
    Notes: Die Reaktion von Verbindungen des Typs [(LZr)(LiH)(L′)]n und [(LZr)(LiH)(L′)(alkin)]n (L: 2,2′-Biphenolato-dianion, L′: thf, Bu3P, alkin: Ph—C≡C—SiMe3, CH≡CH) mit Wasser führt bei 0°C in thf in 50% Ausbeute zum trimeren Bimetallkomplex 8 [(L2Zr)3(μ2-OH)3(μ3-O) Li5(thf)8(H2O)5]. Die Kristallstrukturanalyse von 8 zeigt, daß ein planarer Zr3(μ2-OH)3-Sechsring gebildet wird. In seiner Mitte ist ein dianionisches Sauerstoffatom fixiert, das an den drei L2Zr-Zentren mit planarer μ3-Koordination gebunden ist (Bindungswinkel Zr—O—Zr 120,05°). Fünf Lithiumionen stabilisieren das anionische Gerüst durch Verbrückung der Biphenolatchelatliganden, die mit den Zr-Atomen Chelatsiebenringe ausbilden. 1H-, 13C- und 7Li-NMR-Spektren zeigen, daß in Lösung (thf) die Festkörperstruktur unverändert erhalten bleibt.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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