INTERCALATION-INDUCED REACTIONS OF IRON OXYCHLORIDE

The preparation and structure of the layered complex formed by the intercalation reaction of FeOCl with propargylamine are reported. The solid isolated from this reaction is a crystalline material with a magnetic susceptibility at room temperature of 0.9 x 10(-2) emu g-1 and mu(eff) 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 diffraction and scanning electron microscopy. The preparation of the butylamine intercalate of FeOCl under identical conditions gave only the literature-reported product. The formation of a fine-particle green rust (I) and not the hydrolysis product gamma-FeOOH from the propargylamine complex of FeOCl is suggested based upon magnetic susceptibility. Mossbauer spectroscopy. FTIR, and X-ray powder diffraction evidence. A model to account for the difference in the reactivity and properties of the butylamine and propargylamine complexes of FeOCl is proposed. (C) 1994 Academic Press, Inc.