Chemical syntheses of poly(sulphur nitride), (SN)x

Abstract

Poly(sulphur nitride) is prepared in ca. 65% yield by the reaction of excess of SiMe₃N₃ with S₃N₃Cl₃, S₃N₂Cl₂, or S₃N₂Cl at –15°C in acetonitrile solution. The polymer was also prepared by the reaction of S₃N₃Cl₃ and excess of NaN₃. The preparation of (SN)_x from S₃N₃Cl₃ is dependent on solvent and reaction conditions. Reaction of S₂Cl₂ with NaN₃ in acetonitrile gave a powder containing S₃N₂Cl, S₈, NaCl, and unreacted NaN₃, which when treated with an excess of SiMe₃N₃ in acetonitrile yielded (SN)_x. The (SN)_x polymer was also formed by the reaction of CsN₃ and S₂NAsF₆ in SO₂ at –20 °C. Better quality polymer was prepared from S₃N₃Cl₃, S₃N₂Cl₂, or S₃N₂Cl with excess of SiMe₃N₃, after washing with various solvents. Analogous reactions of Se₂Cl₂ and SeBr₄ gave blue-black explosive solids.