Ligand Control of Reactivity at Metal Centers

无机化学、生物无机化学和金属有机化学计划中的这个项目包括对具有两个多齿配体系统的过渡金属络合物的广泛调查，对冠醚和双核二羧酸盐，主要目的是了解金属离子的性质如何被局部配体环境调节。将对Co、Rh、Fe、Mn、V、Ti和Zr的对冠化合物进行研究，其中链长和金属中心的立体化学的变化预计会影响金属中心的物理性质和反应活性。我们将用不活泼的金属对研究二羧酸盐配体，并考察锌(II)、锰(II)和镁(II)的磷酸酯水解反应。在其他方面，将研究双核早期过渡金属有机金属络合物的C-C键形成反应，并将研究具有氧化还原活性的卟啉环体系中的多电子转移反应。在这项工作中，将探索控制与氮和氧给体原子结合的金属中心的结构和反应活性的基本因素。这些原子受到碳原子骨架的约束，定向增强了金属中心的反应活性。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.