Heteronuclear Fe-Mn Cyclopentadienyl Complexes Supported on Boehmite. Thermochemistry and Thermodynamics of their Decomposition

Abstract

Boehmite samples with compounds of the composition (C5H5)2FeMnX2(μ-CO)n, where X=Cl, Br and n=1.2, precipitated at room temperature from tetrahydrofuran solutions and then heated in an air flow up to 873 K were obtained and characterized using X-ray diffractometry, infrared Fourier spectroscopy, electron magnetic resonance and temperature-programmed desorption methods. It was shown that the thermal decomposition of these compounds applied to the boehmite samples in the range from room temperature to 873 K occurs stepwise and consists of at least two stages. The first stage of thermal decomposition occurs in the range of 453–753 K, and the second – in the range of 813–843 K. The XRD data show that when calcining at 873 K the boehmite samples with the applied compounds of the above composition and containing these compounds less than 10 wt.%, the diffraction patterns show only reflections characteristic of poorly crystallized aluminum oxide. However, the electron paramagnetic resonance (EPR) spectra of these samples clearly show intense signals characteristic of superpara/ferromagnetic particles of iron and manganese oxides, as well as EPR signals from isolated Fe3+ substituting Al3+ ions in the aluminum oxide structure. EPR spectra most of the iron and manganese is stabilized on the surface of poorly crystallized aluminum oxide in the form of nanostructured iron and manganese oxides.