Ligand Control of Reactivity at Metal Centers

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This project in the Inorganic, Bioinorganic, and Organometallic Chemistry Program includes a broad survey of transition metal complexes with two multidentate ligand systems, tropocoronands and binucleating dicarboxylates, with the primary goal of learning how the properties of a metal ion can be tuned by the local ligand environment. Studies of Co, Rh, Fe, Mn, V, Ti, and Zr complexes of the tropocoronands will be performed in which variation in chain length and stereochemistry at the metal center is expected to affect the physical properties and reactivity at the metal center. The dicarboxylate ligands will be studied with labile metal pairs, and the phosphate-ester hydrolysis reactions of Zn(II), Mn(II), and Mg(II) will be examined. Among other things, dinuclear early transition metal organometallic complexes will be examined for their C-C bond-forming reactions, and multielectron transfer reactions in systems with redox-active porphyrin rings will be studied. In this work the fundamental factors controlling structure and reactivity of metal centers bound to nitrogen and oxygen donor atoms will be explored. These atoms are constrained by carbon atom frameworks to orientations which enhance the reactivity at the metal center. These fundamental studies have relevance to areas of bioinorganic chemistry, catalysis, and materials science.