Reaktionen der Lithiumhydridosilylamide Me2(H)Si-N(Li)R (R = CMe3, SiMe3) mit Chlortrimethylstannan und Chlormethylsilanen Me4–nSiCln (n = 1-3)/ Reactions of Lithium Hydridosilylamides Me2(H)Si-N(Li)R (R = CMe3, SiMe3) with Chlorotrimethylstannane and Chloromethylsilanes Me4-nSiCln (n = 1 - 3)
-
Jan Schneider
and
Normen Peulecke
Abstract
The under reflux conditions in n-octane stable lithium hydridosilylamides Me2(H)Si-N(Li)R (1: R = CMe3, 2: SiMe3) were allowed to react with chlorotrimethylstannane and chloromethylsilanes Me4-nSiCln (n = 1 - 3) in different molar ratios.
1 reacts with Me3SnCl in n-pentane to give the cyclodisilazane [Me2Si-NCMe3]2 (3) and Me3SnH. The reaction of 2 with Me3SnCl under the same conditions leads to a mixture of Me2 (H)Si-N(SnMe3)SiMe3 (5), [Me2Si-NSiMe3]2 (4), and to Me3SnH. In the reactions of 1 and 2 with chlorotrimethylstannane in tetrahydrofuran the corresponding N-stannylation products Me2(H)Si-N(SnMe3)R 5, 6 and very small amounts of (Me3Sn)2 are formed.
The results of the reactions of 1 and 2 with Me2SiCl2 and of 1 with MeSiCl3 in n-hexane show that hydrogen-chlorine-exchange proceeds between the reactants. With Me2SiCl2 the corresponding cyclodisilazanes [Me2Si-NR]2 3, 4, N-silylation products Me2(H)Si-N(SiMe2Cl)R 7b, 8b, and Me2(H)Si-N(SiMe2H)R 7c, 8c, and the silanes Me2SiHCl and Me2SiH2 are formed, the cyclodisilazanes being the main products. 1 and MeSiCl3 produce 3, Me2(H)Si-N(R′)CMe3 (7d: R′ = SiMeCl2, 7e: R' = SiMeCIH, 7f: R′ = SiM eH2) and MeSiH3. In comparison with the reaction of 1 with Me2SiCl2 the yield of cyclodisilazane is smaller and that of N-silylated compounds is higher. The reaction behaviour of 1 towards Me2SiCl2 and MeSiCl3 in THF is comparable to that in n-hexane.
No silanimine intermediates are observed in the reactions of 1 or 2 with the chloromethylsilanes Me4-nSiCln (n = 1 - 3) in the molar ratios 1:5 and 1:10.
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