Problems in Bioinorganic and Metal Cluster Chemistry

该项目在无机，生物无机和有机 化学计划是在过渡金属化学领域。 该项目的目的之一是设计化学反应系统 它们是酶促反应的类似物，从而 证明可行的反应途径， 某些酶，如含镍酶 氢化酶和一氧化碳脱氢酶。第二个目标是 使用金属硫簇合物， 材料的种类。 氧转移假说的作用机制， 将通过以下方法进一步研究大类的腺苷酸酶 氧代转移动力学和机理的测定 多种酶底物之间的反应， Mo（VI）/Mo（IV）对。这项工作将有助于 羰基转移热力学标度的发展 反应性和基团转移的定性尺度 反应性也将得到发展。抗氧化反应体系 将开发用于阐明的行动， 镍酶氢化酶和一氧化碳脱氢酶。 基于六钼硫属单体的多簇 将作为化合物的实例合成， 小分子和有序固体之间的中间域， 使用Mo3S4簇的还原缩合或桥连 的衍生集群。簇切除反应， 破坏固体中团簇之间的桥键并将其移除 以衍生形式，将用于获得某些簇， 例如Re6S8，迄今为止，其仅在 高温

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is in the area of transition metal chemistry. One aim of the project is to design chemical reaction systems which are analogues of enzymatic reactions, and thereby to demonstrate feasible reaction pathways for the function of certain enzymes, such as the nickel-containing enzymes hydrogenase and carbon monoxide dehydrogenase. A second aim is to use metal-sulfur cluster compounds to provide access to new types of materials. The oxotransfer hypothesis for the mechanism of action of a broad class of molybdoenzymes will be examined further by determination of the kinetics and mechanisms of oxo transfer reactions between a wide variety of enzyme substrates and Mo(VI)/Mo(IV) couples. This work will contribute to the development of a thermodynamic scale of oxo transfer reactivity, and a qualitative scale for group transfer reactivity will be developed as well. Analogue reaction systems will be developed for the elucidation of the action of the nickel enzymes hydrogenase and carbon monoxide dehydrogenase. Multiclusters based on hexamolybdenumoctachalcogenide monomers will be synthesized as examples of compounds in the intermediate domain between small molecules and ordered solids, using reductive condensation of Mo3S4 clusters or the bridging of derivatized clusters. Cluster excision reactions, which rupture bridge bonds between clusters in solids and remove them in derivatized forms, will be used to obtain certain clusters, such as Re6S8, which thus far have been synthesized only at high temperatures.