Reaction of oxides of nitrogen with some silicon halides and hydride-halides
The interaction of SiF4, Si2F6, SiCl4, Si2Cl6, SiH3I, SiH3Br, SiF3I and p-ClC6H4SiH3 with nitrogen oxides chosen from N2O, NO, N2O3, N2O4, and N2O5 has been studied with and without u.v. irradiation. There is very little reaction between SiF4 and N2O, NO, N2O4, or N2O5 at room temperature. Below ca.–60°, SiF4 reacts with N2O3(but not with N2O4or N2O5) to give a 1 : 1 adduct, probably NO+(SiF4,NO2)–, which dissociates and decomposes above 0°. Both NO and N2O4 react with Si2F6 to produce (SiF3)2O and its disproportionation products, but Si2Cl6 with NO, N2O3, or N2O4, and SiCl4 with NO usually give NOCl and polychloro-siloxanes or -silanes. The iodo-derivatives SiF3I and SiH3I chiefly form disiloxanes and N2O or N2 with NO, but in the former case some oligomeric fluorosiloxanes including cyclic (SiF2O)2are produced with irradiation; SiH3Br and NO yield SiH2Br2 and (SiH2O)n(especially n= 4) under similar conditions. The reaction of SiHCl3 and NOCl produces HCl, N2O, and chloro-siloxanes. No clear evidence for isolable Si-nitroso-compounds was obtained in any system.