(Me3C)2SiF-NCMe3-AlR2, R = Me (5), Et (6) are formed in the reaction of (Me3C)2SiF-NLi CMe3 (I) and ClAlR2. The lithium salt (Me3C)2SiF-NLi-Si(CMe3)2Me (III) reacts with BF3 under formation of the bis(silyl)aminodifluoroborane (Me3C)2SiF-N(BF2) Si(CMe3)2Me (7). In the reaction of I with F3SiPh rotamers of (Me3C)2SiF-NCMe3 SiF2Ph (8) are obtained. Stannyl-silylamines are prepared in reactions of the lithium salts (Me3C)2SiF-NLiR