Fluorsilylsubstituierte Cyclotrisilazane werden bei Umsetzungen von mono‐und dilithiierten 1‐Trimethylsilyl‐2,2,4,4,6,6‐hexamethylcyclotrisilazan mit Fluorsilanen erhalten. In Konkurrenz zur Substitution am Cyclotrisilazan steht in diesen Reaktionen die Substitution und Ringkontraktion unter Bildung strukturisomerer Cyclodisilazane. Die Trennung der isomeren Vier‐und Sechsringsysteme erfolgt gaschromatographisch. Die NMR‐ und Massenspektren der Verbindungen werden mitgeteilt.
Abstract Hexamethylcyclotrisilazanes and their lithium salts react with F2BN(SiMe3)2 to give the corresponding mono-, bis-, and tris(fluoroboryl)cyclotrisilazanes. Di-fluoroboryl-substituted rings are obtained in the reaction of 1,3-bis(silyl)- and 1-boryl-cyclotrisilazanes with BF3-etherate. A compound consisting of two cyclodisilazanes connected by a (SiNBNSi)-bridge is formed in the reaction of lithiated bis(silyl)cyclotrisilazane with BF3-etherate. Ring coupling of two six membered rings occurs in the reaction of lithiated cyclotrisilazane with 1-difluoroboryl-cyclotrisilazane and in the reaction of lithiated bis(fluoroboryl)cyclotrisilazane with BF3-etherate in a molar ratio 2:1. Ring expansion takes place in the reaction of the lithium salt of a four membered SiN-ring with F2BN(SiMe3)2. Substitution occurs in the same reaction with F3SiN(SiMe3)2.
Abstract Phosphaethenes of the type (Me3Si)2C = P -NRSiMe3 R = C10H15 (7), CMe3 (8), 2.4.6-Me3C6H2 (10)), LiF, and Me3SiF are obtained in the reaction of the aminodifluorophosphanes (3-5) with the lithium salt of tris(trimethylsilyl)methane (1). 10 is isolated as by-product. The main product is F2PC(SiMe3)3 (9). The lithium salt of tris(trimethylsilyl)silan (2) reacts with 3 -6 to give the thermally stable substitution compounds (Me3Si)3Si -PF-NRSiMe3 (11-14). The fluorosilylphosphane Me3Si(CMe3)P -SiFMe - N(SiMe3)2 (15) is formed in the reaction of Me3Si(CMe3)PLi and F2SiMeN (SiMe3)2.
1‐(Fluordimethylsilyl)‐3‐lithio‐2,2,4,4,6,6‐ hexamethyl‐5‐(trimethylsilyl)cyclotrisilazan (1) reagiert mit H‐aciden Verbindungen wie ROH und R′C CH im Molverhältnis 1:1 zu den substituierten Verbindungen 2, 3 (RC2H5, CH3), 7 (R′n‐C4H9) und LiF. Ringkontraktion zu viergliedrigen Ringen wird in analoger Reaktion für die Substituenten RCH3 (4), C6H5 (5) sowie R′n‐C4H9 (8) und C6H5 (9) beobachtet.
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