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    ISSN: 0044-2313
    Keywords: Carbosilanes ; Cu-catalyzed reactions of silicon with C-chlorinated 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexanes ; crystal structures of hexadecachloro-1,3,5,7,9,11,13,14-octasiladispiro[5.1.5.1]tetradecane ; decachloro-1,3,5,7,9,11-hexasilatricyclo[6.4.0.02,7]dodecane and decachloro-2-trichlorosilyl-1,3,5,7,9,11-hexasilatricyclo[6.4.0.02,7]dodecane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Organosilicon Compounds 113. Reactions of C-chlorinated 1,1,3,3,5,5-Hexachloro-1,3,5-trisilacyclohexanes with Si(Cu cat.). Structures of Hexadecachloro-1,3,5,7,9,11,13,14-octasiladispiro[5.1.5.1]tetradecane 12, Decachloro-1,3,5,7,9,11-hexasilatricyclo[6.4.0.02,7]dodecane 13 and Decachloro-2-trichlorosilyl-1,3,5,7,9,11-hexasilatricyclo[6.4.0.02,7]dodecane 14Elemental Si(Cu cat.) was treated with 1,1,2,2,3,3,5,5-octachloro-1,3,5-trisilacyclohexane 3, 1,1,2,2,3,3,4,4,5,5-decachloro-1,3,5-trisilacyclohexane 4 and with (Cl2Si—CCl2)3 5, resp., in a stirred bed reactor at 330°C. The products can be understood as to be formed by silylation, hydrogenation, degradation, rearrangement and condensation reactions all of them starting from the CCl2 groups of the trisilacyclohexanes. Especially remarkable is Si8C6H8Cl16 12 with a C-spiro linked framework formed by a trisilacyclohexane, a disilacyclobutane and another trisilacyclohexane building block. In two further tricyclic carbosilanes Si6C6H10Cl10 13 and Si7C6H9Cl13 14, two trisilacyclohexane rings each share an opposite Si—C bond with a disilacyclobutane. Another group of compounds includes compounds consisting of two 1,3,5-trisilacyclohexane rings linked by either a C=C or a C=C=C unit. Moreover some derivatives of 1,3-disilacyclopentenes are formed obviously by a contraction of the C-chlorinated 1,3,5-trisilacyclohexane rings. Compound 12 crystallizes in the monoclinic space group P21/n (no. 14) with a = 1 307.8, b = 1 184.2, c = 984.4 pm, β = 93.58° and Z = 2 molecules per unit cell. 13 crystallizes in the triclinic space group P1 (no. 2) with a = 885.7, b = 911.6, c = 868.3 pm, α = 113.15°, β = 75.36° γ = 119.22° and Z = 1. 14 crystallizes in the monoclinic space group P21/c (no. 14) with a = 1853.2, b = 912.9, c = 1725.3 pm, β = 112.69° and Z = 4.
    Notes: 1,1,2,2,3,3,5,5,-Octachlor-1,3,5-trisilacyclohexan 3, 1,1,2,2,3,3,4,4,5,5-Decachlor-1,3,5-trisilacyclohexan 4 und (Cl2Si—CCl2)3 5 wurden mit Si(Cu) bzw. Cu im Rührbett bei 330°C umgesetzt. Die Reaktionen gehen von den CCl2-Gruppen der Trisilacyclohexane aus, und die verschiedenen Reaktionsprodukte sind durch Silylierung, Hydrierung, Kondensation und Umlagerung zu erklären. Besonders bemerkenswert ist das Si8C6H8Cl16 12, in dessen Grundgerüst zwei 1,3,5-Trisilacyclohexane über einen Disilacyclobutanring C-spiroverbrückt sind. In zwei tricyclischen Carbosilanen, Si6C6H10Cl10 13 und Si7C6H9Cl13 14, sind zwei Trisilacyclohexane über einen Disilacyclobutanring verbunden, der unter Ausbildung von zwei Si—C-Bindungen zwischen gegenüberliegenden SiCl- und CCl-Gruppen aufgebaut ist. Eine weitere Gruppe enthält Verbindungen, in denen zwei 1,3,5-Trisilacyclohexanringe entweder über eine C=C- oder C=C=C-Gruppe verbunden sind. Es entstehen auch 1,3-Disilacyclopentenderivate, deren Bildung auf eine Ringverengung der C-chlorierten 1,3,5-Trisilacyclohexane zurückgeführt wird. Verbindung 12 kristallisiert monoklin in der Raumgruppe P21/n (Nr. 14) mit a = 1 307,8, b = 1 184,2, c = 984,4 pm, β = 93,58° und Z = 2 Molekülen pro Elementarzelle; 13: triklin in der Raumgruppe P1 (Nr. 2) mit a = 885,7, b = 911,6, c = 868,3 pm, α = 113,15°, β = 75,36°, γ = 119.22° und Z = 1; 14: monoklin in der Raumgruppe P21/c (Nr. 14) mit a = 1 853,2, b = 912,9, c = 1 725,3 pm, β = 112.69° und Z = 4.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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