Synthesis and characterization of a dinuclear ferric complex with redox-active ligands |
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Authors: | Gabriele Heinze-Brü ckner |
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Affiliation: | Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany |
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Abstract: | A dinuclear ferric complex with the redox-active ligand (LCl2)2- (H2LCl2 = N,N′-dimethyl-bis(3,5-dichloro-2-hydroxybenzyl)-1,2-diaminoethane), was synthesized and characterized. The two iron(III) ions are six-coordinate in a distorted octahedral environment of the donor set of one (LCl2)2− and one amine and one phenolate donor of a second (LCl2)2−, which bridges the two complex halves. The relatively low-symmetric complex 1 crystallizes in the space group R. The crystal structure contains hexagonal, one-dimensional channels parallel to the c axis with diameters of ∼13 Å. The absorption spectrum of 1 exhibits strong characteristic features of pπ → dπ∗, pπ → dσ∗, phenolate-to-metal CTs, and π → π∗ ligand transitions. Electrochemical studies on 1 reveal the redox-activity of the coordinated ligand (LCl2)2− by showing irreversible oxidative electron-transfer waves. The reductive electron transfers at negative potentials seem to originate from metal-centered processes. A detailed comparison to complexes with similar donor sets provides new insights into the electrochemical properties of these kinds of complexes. |
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Keywords: | Bioinorganic chemistry Electrochemistry Non-innocent ligands Iron complexes |
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