O-HALOGENOSILYL-N,N-BIS(TRIMETHYLSILYL)HY DROXYLAMINES - SYNTHESIS, CRYSTAL-STRUCTURE, AND REACTIONS

The substitution of halogenosilanes on lithiated N,O-bis(trimethylsily l)-hydroxylamine in the molar ratio of 1:1 occurs on the oxygen atom. The alogenasilyl-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 = C 6H2Me3, R' = C6H2Me3 7; R = CH2C6H5, R' = CH2C6H5 8; R = CHMe2, R' = C HMe2 9; R = CMe3, R' = CMe3 10), RSiCl2ON(SiMe3)(2) (R = CMe3 11; R = Cl 12). The reaction of fluorosilanes with lithiated N,O-bis(trimethyl silyl)hydroxylamine in the molar ratio of 1:2 leads to the formation o f rosilyl-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 struc ture of a tris(silyl)hydroxylamine (4) is shown. The angle at the nitr ogen prove a pyramidal geometry.