Ligand Control of Reactivity at Metal Centers

该项目属于无机、生物无机和有机金属化学专业，包括对两种多齿配体系统（对偶冠体和双核二羧酸）的过渡金属配合物的广泛调查，其主要目标是了解金属离子的性质如何通过局部配体环境进行调节。对Co， Rh, Fe, Mn， V， Ti和Zr的对偶冕配合物的研究将进行，其中链长和金属中心立体化学的变化预计会影响金属中心的物理性质和反应性。二羧酸配体将与不稳定的金属对进行研究，并研究Zn(II), Mn（II）和Mg（II）的磷酸酯水解反应。除其他外，双核早期过渡金属有机金属配合物将被检查其C-C键形成反应，和多电子转移反应系统与氧化还原活性卟啉环将被研究。在这项工作中，控制结构和反应性的基本因素结合的金属中心氮和氧的供体原子将探讨。这些原子受到碳原子框架的约束，取向增强了金属中心的反应性。这些基础研究涉及生物无机化学、催化和材料科学等领域。

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.