Problems in Bioinorganic and Metal Cluster Chemistry

这个项目属于无机、生物无机和有机金属化学专业，属于过渡金属化学领域。该项目的目的之一是设计类似于酶反应的化学反应系统，从而证明某些酶功能的可行反应途径，例如含镍酶氢化酶和一氧化碳脱氢酶。第二个目标是利用金属-硫簇化合物提供获取新型材料的途径。通过确定各种酶底物和Mo(VI)/Mo（IV）偶对之间的氧转移反应的动力学和机制，将进一步检验一类钼酶作用机制的氧转移假说。这项工作将有助于氧转移反应性的热力学尺度的发展，以及基团转移反应性的定性尺度的发展。将开发模拟反应体系来阐明镍酶氢化酶和一氧化碳脱氢酶的作用。在小分子和有序固体之间的中间区域，利用Mo3S4簇的还原性缩合或衍生化簇的桥接，将合成基于六聚多聚三甲醇系单体的多簇化合物。团簇去除反应，即破坏固体团簇之间的桥键并以衍生形式去除它们，将用于获得某些团簇，如Re6S8，迄今为止仅在高温下合成。

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.