O-Halogensilyl-N,N-bis(trimethylsilyl)hydroxylamine – Synthese,Kristallstruktur und Reaktionen

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-bis[N,N-bis(trimethylsilyl)hydroxylamines]: RSiF[ON(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.