PREPARATIVE AND SPECTROSCOPIC STUDIES ON VOLATILE SILYLHYDROXYLAMINESAND ALKYLHYDROXYLAMINES

(Hydridosilyl)hydroxylamines have been prepared from the corresponding chloro- and bromosilanes and alkylated hydroxylamines in the presence of an auxiliary base (NEt3, TMEDA). Dimethylsilyl groups were introdu ced in order to obtain open chain silylhydroxylamines, while alpha,ome ga-disilylalkane groups were employed for cyclic species. In mass spec tral studies a nitrene extrusion was found to be one of the main fragm entation processes. N-15, O-17 (and H-1, C-13, Si-29) heteronuclear NM R studies were carried out for a larger series of silylated and alkyla ted hydroxylamines. The O-17 and N-15 chemical shifts are clearly dist inguished from those of other compounds containing saturated nitrogen and oxygen centers. The one bond coupling constants 1J((NSi)-N-15-Si-2 9) indicate a pyramidal coordination of nitrogen in silylhydroxylamine s.