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Abstract
Abstract Depending on the reaction conditions lithium derivatives of hexamethylcyclotrisilazanes (HMCTS) react with fluorosilanes to give N-substitution products (1–7). Ring coupling of two six-membered rings by a silyl bridge (8) and of one six-membered and one four-membered ring by a SiNSi-bridge (9) are achieved in the reaction of lithiated HMCTS (1) with a F3Si-substituted HMCTS (4). Two (10) and three (11) six-membered rings coupled by a Si(H)Me-group are formed in the reaction of lithiated HMCTS and FSi(H)Me-substituted HMCTS. Ring contraction of the lithium derivative of the bis(fluorodimethylsilyl)-HMCTS occurs in solution. A compound with three silyl-bridged cyclodisilazanes (12) is obtained. A bicyclic compound (13) is formed in the reaction of the lithium derivatives of the isomeric Me3Si-and FSi(H)Me-substituted six-and four-membered rings. The mechanism of this process is discussed. The compounds have been characterised by NMR spectroscopy. In Abhängigkeit von den Reaktionsbedingungen reagieren Lithiumderivate des Hexamethylcyclotrisilazans (HMCTS) mit Fluorsilanen unter Substitution am lithiierten N-Atom (1–7). Ringkopplungen zweier sechsgliedriger Ringe über eine Silylgruppe (8) sowie eines sechs-und eines viergliedrigen Ringes über eine SiNSi-Brücke (9) erfolgen in der Reaktion des lithiierten HMCTS (1) mit einem F3Si-substituierten HMCTS (4). Die Reaktion von lithiiertem HMCTS mit FSi(H)Mesubstituierten HMCTS führt zur Verknüpfung von zwei (10) und drei (11) sechsgliedrigen Ringen über Si(H)Me-Gruppen. Das Ringsystem des Lithiumderivats des Bis(fluordimethylsilyl)-substituierten HMCTS kontrahiert in Lösung. Eine Verbindung mit drei silylverbrückten Cyclodisilazanen (12) wird gebildet. Eine bicyclische Verbindung (13) entsteht in der Reaktion der Lithiumderivate der isomeren, Me3Si-und FSi(H)Mesubstituierten sechs-und viergliedrigen Ringe. Der Bildungsmechanismus wird diskutiert. Die Verbindungen wurden NMR-spektroskopisch charakterisiert.
Published Version
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