Reaction of metallic indium with benzoyl peroxide in 4-methylpyridine (4-Mepy) at 25 °C produces an eight-coordinate mononuclear indium(III) benzoate, In(η2-O2CC6H5)3(4- Mepy)2 4H2O (I), in yields of up to 60%. The indium(III) benzoate was fully characterized by elemental analysis, spectroscopy, and X-ray crystallography; (I) exists in the crystalline state as discrete eight-coordinate molecules; the coordination sphere around the central indium atom is best described as pseudo-square pyramidal. Thermogravimetric analysis of (I) and X-ray diffraction powder studies on the resulting pyrolysate demonstrate that this new benzoate is an inorganic precursor to indium oxide. Decomposition of (I) occurs first by loss of 4-methylpyridine ligands (100°-200°C), then loss of benzoates with formation of In2O3 at 450°C. We discuss both use of carboxylates as precursors and our approach to their preparation.
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