Mechanistic Studies of Oxygen Evolution and Hydrogen Atom Transfer in Enzymes and Biomimatic Models

该奖项在无机、生物无机和有机金属化学项目中支持普渡大学Mahdi Abu-Omar教授的研究，研究金属介导的氢原子转移（HAT）和与绿泥石歧化酶有关的反应。HAT化学的目标是：(1)研究一系列含锰、铬和钒的六苯胺配合物及其氧类似物中氢原子转移（HAT）的动力学和机制；(2)利用这些新型的亚胺配合物扩大HAT的应用，以实现C-H键的催化胺化。第二个项目涉及由高氯酸盐呼吸细菌形成的亚氯酸盐离子（ClO2 -）的反应化学（分解/破坏）。本文将研究亚氯酸dismuatse酶（Cld）中亚氯酸dismuatse酶的机理，并与水溶性类卟啉模型进行比较。了解金属介导的HAT反应的反应速率和机理，有助于利用这些反应实现C-H键的良性功能化。在酶和模型中对亚氯酸盐分解的研究对环境中氯氧离子的化学性质有重要影响。博士后、研究生和本科生研究人员将学习制造分子、测量动力学、进行最先进的光谱实验、分析数据以获得分子（机制）洞察力，并展示他们的研究成果。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Mahdi Abu-Omar at Purdue University to investigate metal mediated hydrogen atom transfer (HAT) and to study the reactions involved with chlorite dismutase. The objectives of the HAT chemistry are to: (1) study the kinetics and mechanism(s) of hydrogen atom transfer (HAT) in a series of tosylimido complexes of corrole (Mn, Cr, and V) and their oxo analogs, and (2) expand the utility of HAT with these novel imido complexes to achieve catalytic amination of C-H bonds. A second project is concerned with the reaction chemistry (dismutation/destruction) of the chlorite ion (ClO2 -), which is formed by perchlorate respiring bacteria. The mechanism of chlorite dismutation in the enzyme chlorite dismuatse (Cld) will be studied and compared with water soluble prophyrinoid models. Understanding reaction rates and mechanisms of metal mediated HAT reactions relates to harnessing these reactions for benign functionalization of C-H bonds. The study of chlorite dismutation in enzyme and models has ramifications for the chemistry of chloride oxyanions in the environment. Postdoctoral, graduate, and undergraduate researchers will learn to make molecules, measure kinetics, perform state-of-the art spectroscopic experiments, and analyze data to gain molecular (mechanistic) insight, and present their research findings.