Traegergebundene Metallporphyrine als Oxidationskatalysatoren Schlussbericht

Abstract

In a joint venture with Degussa AG, singly or quadruply functionalized tetraarylporphyrins and their respective manganese(III) complexes were synthesized. Their potential as catalysts for the oxidation of organic compounds with hydrogen peroxide was tested. The manganese porphyrins were checked both in homogeneous and heterogeneous phase. Heterogeneous phases were obtained by fixation of manganese porhyrins to organic or mineral supports, e.g. via covalent bonds for chloromethylpolystyrene, secondary aminopolysiloxanes, or aminopropyl silica gel, or via ionic bonds for anion exchange resins. For these purposes, the following residues were attached to porphyrins and their chloromanganese(III) complexes: chlorosulfonyl or chlorocarbonyl for covalent fixation, sulfonate or carboxylate for ionic fixation. The complexes were characterized by UV/Vis-, IR-, NMR- and mass spectra. The ionic derivatives were purified by electrophoresis or ultrafiltration. Supported manganese(III) porphyrins were transformed into nitridomanganese(V) derivatives which were identified by UV/Vis diffuse reflectance spectroscopy. The screening of the new manganese porphyrin phases was done by Degussa. Tetraphenylporphyrin, tetrakis(o,o'-dichlorophenyl)porphyrin, or tetrakis(o,o'-dichlorophenyl)octachloroporphyrin were subjected to functionalizations. Procedures for direct monofunctionalization of the two porphyrins mentioned in the first place were elaborated. (orig.)SIGLEAvailable from TIB Hannover: F95B1642+a / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Forschung und Technologie (BMFT), Bonn (Germany)DEGerman