INTERCALATION-INDUCED REACTIONS OF IRON OXYCHLORIDE

The preparation and structure of the layered complex formed by the int ercalation reaction of FeOCl with propargylamine are reported. The sol id isolated from this reaction is a crystalline material with a magnet ic susceptibility at room temperature of 0.9 x 10(-2) emu g-1 and mu(e ff) 18 BM. Reaction of this complex by heating under argon by exposure to moist air, or by washing with water results in new materials with larger susceptibilities, 1.8 x 10(-2) emu g-1, and mu(eff) 72 BM, but with a more disordered structure as determined by X-ray powder diffrac tion and scanning electron microscopy. The preparation of the butylami ne intercalate of FeOCl under identical conditions gave only the liter ature-reported product. The formation of a fine-particle green rust (I ) and not the hydrolysis product gamma-FeOOH from the propargylamine c omplex of FeOCl is suggested based upon magnetic susceptibility. Mossb auer spectroscopy. FTIR, and X-ray powder diffraction evidence. A mode l to account for the difference in the reactivity and properties of th e butylamine and propargylamine complexes of FeOCl is proposed. (C) 19 94 Academic Press, Inc.