The disilanol (CMe3)2Si(OH)2 (1) serves as a starting material in the reaction with C4H9Li and sodium for the construction of the alkali derivatives 2,3,4, and the siloxanes 5,6,7,8. The six-membered cyclosiloxane 10 and the spirocyclic compound 11 are easily prepared in the reaction of [(Me3C)2Si(OH)]2O (8) with 2C4H9Li and SiF4 or SnBr4. The crystal structures of (Me3C)2Si(OLi)2 (3), (Me3C)2Si(ONa)OH (4), and (Me3C)2Si(ONa)OSiF(Me3C)2 (9) have been determined and are discussed.
Lithiated text‐butylaminolfluorosilanes react with aluminum trichloride in ether, eliminating LiF to give AlCl3 adducts of iminosilanes — aminosiliceniotrichloroaluminates {R2Si‐NCMe3·AlCl3}, which thermally form the dimethylazomethine‐ aluminium trichloride, Me2CNH·AlCl3.
Dilithium derivatives of bis(silylamino)fluorosilanes (1-3) react with chlorotrimethylsilane to give dilithium derivatives of the corresponding bis(silylamino)chlorosilanes and Me3SiF. LiCl-elimination in the presence of THF leads to the formation of silaamidides, which are isolated as dimers, four-membered cyclosilazane anions. (R′Si-NR)2Li(NR)2㊀’, Li(THF)4㊉ (4, 6), and (THF)3Li-ClLi(THF)3㊉ (5) cations. Hydrolysis of the dimeric silaamidides is the only but facile synthesis of cyclodisilazanes in cis-conformation (7 - 9). 1, 4, 7: R = Si(CMe3)2Me, R′= F; 2. 5. 8: R = SiMe2CMe3, R′= CMe3; 3, 6, 9: SiMe2CMe3, R = C6H5.
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