Thermal initiation ( 300°C) of a reaction between sodium azide and anhydrous metal chlorides (LaCl 3 , SmCl 3 , TiCl 3 , ZrCl 4 , HfCl 4 , VCl 3 , TaCl 5 , CrCl 2 , WCl 6 and MnCl 2 ) in sealed evacuated ampoules rapidly produces binary metal nitrides, dinitrogen and sodium chloride. The metal nitrides were purified by trituration with methanol and characterized by powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and FT-IR.