Magnesium and Calcium Nitrides as Nitrogen Sources in Metathetical Reactions to Produce Metal Nitrides

Abstract

Reaction of Ca 3 N 2 or Mg 3 N 2 with anhydrous metal chlorides (MnCl 2 ; MCl 3 , M = Ti, V, Mo, Nd, Sm, Gd, Tb, Er; MCl 4 , M = Hf, W; MCl 5 , M = Nb, Ta) in evacuated sealed Pyrex or quartz ampules at 500-900 °C or by filament initiation under nitrogen or argon was used to produce metal nitrides and calcium or magnesium chloride. The nitrides were purified by washing with methanol and isolated in ca. 70-90% yield. Variation in reaction conditions allowed the isolation of intermediate phazes of Ln 2 Cl 3 N (Ln = Sm, Gd, Tb, Er) and Ca 2 NCl, giving evidence that at least some of the reactions proceed via ionic metathesis pathways. Phase-pure VN and V 2 N were produced, both of which have previously been inaccessible in solid-state reactions using metathetical methods. © 1995, American Chemical Society. All rights reserved.