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  • 1
    ISSN: 0044-2313
    Keywords: Lithiumhydridosiloxysilylamides ; reaction behaviour ; N-silylation ; Si—O bond splitting ; cyclodisilazanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lithium Hydridosiloxysilylamides - Reactions in n-Octane and Tetrahydrofuran in Presence of ChlorotrimethylsilaneThe hydrido-siloxy-silylamino-silanes (Me3SiO)HSiMe(NHSiMe3) 1, (Me3SiO)HSi(NHSiMe3)2 2 and (Me3SiO)2HSi(NHSiMe3) 3 were prepared by coammonolysis of the chlorosiloxysilanes (Me3SiO)HSiMeCl and (Me3SiO)3-nHSiCln (n = 1, 2) with chlorotrimethylsilane. The reaction behaviour of lithiated compounds 1, 2 and 3 has been investigated in n-octane and tetrahydrofuran (THF) in presence of chlorotrimethylsilane.
    Notes: Durch Koammonolyse der Chlorsiloxysilane (Me3SiO)HSiMeCl und (Me3SiO)3-nHSiCln (n = 1, 2) mit Chlortrimethylsilan wurden die Hydrido-siloxy-silylamino-silane (Me3SiO)HSiMe(NHSiMe3) 1, (Me3SiO)HSi(NHSiMe3)2 2 und (Me3SiO)2HSi(NHSiMe3) 3 dargestellt und das Reaktionsverhalten der lithiierten Verbindungen 1, 2 und 3 in n-Octan und Tetrahydrofuran (THF) in Gegenwart von Chlortrimethylsilan untersucht.Sowohl das Monoamid (Me3SiO)HSiMe(NLiSiMe3) als auch das Diamid (Me3SiO)HSi(NLiSiMe3)2 reagieren unter N-Silylierung zu N-Substitutionsprodukten und unter Si—O-Bindungsspaltung und LiOSiMe3-Eliminierung zu Cyclodisilazanen, wobei THF die N-Silylierung, n-Octan die Bildung von Cyclodisilazanen begünstigt. Das Monoamid ergibt in n-Octan (Me3SiO)HSiMe[N(SiMe3)2] 4, [Me(H)Si-NSiMe3]2 5 (Hauptprodukt) und 6, in THF 4 als Hauptprodukt und 5. Aus dem Diamid werden in THF (Me3SiO)HSi[N(SiMe3)2](NHSiMe3) 7, bevorzugt (Me3SiO)HSi[N(SiMe3)2]2 8, [(Me3SiNH)HSi—NSiMe3]2 9 und 10 gebildet, in n-Octan 7, bevorzugt 9 und 10.Hauptprodukt der Reaktion des Amids (Me3SiO)2HSi(NLiSiMe3) in THF und n-Octan ist das N-Silylierungsprodukt (Me3SiO)2HSiN(SiMe3)2 11.Eine Reaktion unter Beteiligung der Si—H-Gruppe wird nur im Falle von (Me3SiO)HSiMe(NLiSiMe3) beobachtet, Produkt dieser Reaktion ist 6.The monoamide (Me3SiO)HSiMe(NLiSiMe3) and the diamide (Me3SiO)HSi(NLiSiMe3)2 react under N-silylation to N-substitution products and under Si—O-bond splitting and LiOSiMe3-elimination to cyclodisilazanes in n-octane as well as in THF. The favour reaction is in THF the N-silylation, in n-octane the formation of cyclodisilazanes. The monoamide gives in n-octane (Me3SiO)HSiMe[N(SiMe3)2] 4, [Me(H)Si-NSiMe3]2 5 (main product) and 6, in THF as main product 4 and 5. The diamide reacts in THF to give (Me3SiO)HSi[N(SiMe3)2](NHSiMe3) 7, mainly (Me3SiO)HSi[N(SiMe3)2]2 8, [(Me3SiNH)HSi—NSiMe3]2 9 and 10, in n-octane 7, mainly 9 and 10.The N-silylation product (Me3SiO)2HSiN(SiMe3)2 11 is the main product of the reaction of (Me3SiO)2HSi(NLiSiMe3) in THF and in n-octane.A reaction with participation of the Si-H group is only observed in the case of (Me3SiO)HSiMe(NLiSiMe3). 6 is the product of this reaction.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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