Synthesis and Properties of Metal-Sulfur Clusters Consisting of Multiple Components

氮气和一氧化碳的生物转化分别由称为固氮酶和一氧化碳脱氢酶的金属酶介导。它们的活性中心由硫、铁和另一种过渡金属组成，其复杂的结构一直是挑战合成目标的因素。在本研究项目中，我们开发了在非极性有机溶剂中合成Fe/S/O和V/Fe/S团簇的新反应。该项目的一个重要成果是合成了模拟固氮酶活性部位的[Fe8S6O]簇。其中心氧原子的成键方式为我们理解酶活性部位的工作原理提供了线索。还需要注意的是[VFe3S4-Fe]簇的合成，它在结构上与CO脱氢酶的活性位置有关。

Biological transformations of N2 and CO are mediated by the metallo-enzymes called nitrogenase and CO-dehydrogenase, respectively. Their active sites consist of sulfur, iron, and another transition metal, and their complex structures have been challenging synthetic targets. In this research project, we developed new synthetic reactions for Fe/S/O and V/Fe/S clusters in non-polar organic solvents. One of the important outcomes of this project is the synthesis of the [Fe8S6O] cluster which mimics the active site of nitrogenase. The bonding mode of its central oxygen atom gave us a clue to understand how the enzymatic active site works. Also to be noted is the synthesis of [VFe3S4-Fe] cluster which is structurally relevant to the active site of CO-dehydrogenase.