| Abstract: | O-Halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines – Synthesis, Crystal Structure, and Reactions The substitution of halogenosilanes on lithiated N,O-bis(trimethylsilyl)-hydroxylamine in the molar ratio of 1 : 1 occurs on the oxygen atom. The O-halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines were prepared: RSiF2ON · (SiMe3)2 (R = CMe3 1 , CHMe2 2 , CH2C6H5 3 , C6H2(CMe3)3 4 ), RR′SiFON(SiMe3)2 (R = CMe3, R′ = C6H5 5 ; R = Me, R′ = C6H5 6 ; R = C6H2Me3, R′ = C6H2Me3 7 ; R = CH2C6H5, R′ = CH2C6H5 8 ; R = CHMe2, R′ = CHMe2 9 ; R = CMe3, R′ = CMe3 10 ), RSiCl2ON(SiMe3)2 (R = CMe3 11 ; R = Cl 12 ). The reaction of fluorosilanes with lithiated N,O-bis(trimethylsilyl)hydroxylamine in the molar ratio of 1 : 2 leads to the formation of O,O′-fluorosilyl-bisN,N-bis(trimethylsilyl)hydroxylamines]: RSiFON(SiMe3)2]2 (R = CMe3 13 ; R = C6H5 14 ). 13 could be prepared in the reaction of 1 with LiON(SiMe3)2. Lithiated dimethylketonoxime reacts with 1 to Me2C=NOSiRF–ON(SiMe3)2 R = CMe3 ( 15 )]. The first crystal structure of a tris(silyl)hydroxylamine ( 4 ) is shown. The angle at the nitrogen prove a pyramidal geometry. |
