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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of cluster science 9 (1998), S. 63-91 
    ISSN: 1572-8862
    Keywords: Hexanuclear zirconium cluster ; pentanuclear zirconium cluster ; cluster hydrogen atom ; bromide ; chloride ; arsine ; amine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Reduction of ZrBr4 with HSnBu3 yielded a blue solid. When this blue solid was treated with PMe3, a hexanuelear cluster [Zr6Br14H4( PMe3)4] (2) was isolated. Reaction of the blue solid with [PPh4]Br in CH2Cl2 resulted in the formation of a paramagnetic and unstable cluster anion, [Zr6Br18H5]2− (3′), which disproportionated to form a new cluster anion, [Zr6Br18H5]3− (4′) and some Zr(IV) species. Compounds containing 4′ can also be obtained from reaction of the blue solid with Br− in MeCN. Reduction of ZrCl4 with HsnBu3 gave a red–brown solid, and [Zr6Cl14H4(AsMe3)4] (9) and [Zr5Cl12H4(AsMe3)5](8) were obtained by reaction of the red–brown solid with AsMe3. No cluster compounds containing amine ligands were obtained in the reaction of the red–brown solid with amines; only compounds containing the [Zr6Cl18 H5]3− anion and ammonium cations were isolated. Altogether ten products were characterized by single crystal X-ray diffraction and where possible, by 1H NMR studies.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of cluster science 6 (1995), S. 411-419 
    ISSN: 1572-8862
    Keywords: Rhenium ; metallocycle ; cluster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The compound (n-Bu4N)2[Re4Cl8(μ-Cl)2(μ-O)2 · 2THF] has been prepared from (n-Bu4N)2 Re2Cl8 by refluxing it in wet trifluoroacetic acid. It forms brown, block-shaped crystals in space group P $$\bar 1$$ , withZ = 2 in a cell of dimensions:a = 11.748(1) Å,b = 16.847(3) Å,c = 16.953(3) Å, α = 97.53(1)°β = 106.49(1)° γ = 101.25(1)°V = 3093(1) Å3. There are two independent but practically identical tetranuclear anions, each on a crystallographic inversion center. The short, unbridged Re-Re edges, to which triple bonds are assigned have lengths of 2.280(1) Å and 2.276(1) Å and the longer edges, each with a μ-Cl and a μ-O atom have lengths of 2.611(1) Å and 2.615(1) Å, for molecules 1 and 2 respectively. This anion completes a series going from [Re4Cl8(μ-O)2(μ-OMe)2]2− through [Re4Cl8(μ-O)2(μ-OMe)(μ-Cl)]2− to the present [Re4Cl8(μ-O)2(μ-Cl)2]2−. These metallocyclobutadiynes can be viewed as products of the 2,2-cycloaddition of two Re-Re quadruple bonds, but the mechanistic details of how they arise remain obscure.
    Type of Medium: Electronic Resource
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