CAREER: Nitrogen/Sulfur Clusters of Iron: Synthetic Approaches to Nitrogenase Chemistry

这项无机化学、生物无机化学和金属有机化学项目的职业奖支持普林斯顿大学化学系的Sonny Lee教授对固氮酶中铁-硫辅助因子作用机制的研究。这种辅因子被认为是将氮素还原为氨的，但其作用方式尚不清楚。将采用两种互补的方法来获得有关机理的信息：(1)将研究亚胺铁(II)立方烷簇合物的反应化学，特别是簇合物形成中的氮-氮键断裂和簇合物催化的歧化反应；(2)将合成新的铁-氮-硫配合物并对其反应活性进行表征。这项研究的目的是确定金属(铁)簇在固氮酶中的作用。本研究的目的是确定金属(铁)簇在固氮酶中的作用。这些酶为生物提供固定的大气氮，但这一过程的化学成分仍然是一个谜。本研究的结果将有助于确定这一关键的酶过程的机理。此外，所获得的知识可用于设计人工系统，在比当前工业过程温和得多的条件下，将空气中的氮转化为氨和其他有用的化合物。将开发一门结合研究主题和合作学习的新课程，以及一项面向该地区公立学校的外展计划，这些学校由普林斯顿的学生教师和当地的工业科学家组成。这些活动将有助于对研究生和本科生进行多学科培训，并提高中小学的科学教育和公众科学意识。

This CAREER award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research on the mechanism of action of the iron-sulfur cofactor in nitrogenase enzymes, by Professor Sonny Lee of the Department of Chemistry at Princeton University. This cofactor is believed to carry out the reduction of dinitrogen to ammonia, but its mode of action is unknown. Two complementary approaches will be employed to obtain information on the mechanism: (1) the reaction chemistry of imidoiron(II) cubane cluster compounds, in particular nitrogen-nitrogen bond cleavage in cluster formation and disproportionation reactions catalyzed by the clusters, will be investigated and; (2) new iron-nitrogen-sulfur complexes will be synthesized and their reactivities characterized. Clusters containing a new class of sterically-hindered, chelating thiolate/thioether ligands will also be synthesized and their activation of nitrogen-nitrogen double and triple bonds examined.The goal of this research is to determine how a metal (iron) cluster in the nitrogenase enzymes functions. These enzymes provide fixed atmospheric nitrogen to living organisms, but the chemistry of this process remains a mystery. The results of this study will help to determine the mechanism of this critical enzymatic process. In addition, the knowledge gained can be used in the design of artificial systems to convert nitrogen from the air into ammonia and other useful compounds under much milder conditions than in current industrial processes. A new course combining research topics and cooperative learning will be developed, as well as an outreach program to the area public schools staffed by Princeton student-teachers and local industrial scientists. These activities will assist in the multidisciplinary training of both graduate and undergraduate students, and improve science education and public awareness of science in the primary and secondary schools.