Presidential Young Investigator: Synthesis and Reactivity of Vanadium(II) Coordination Compounds

这项由无机化学、生物无机化学和有机金属化学计划颁发的总统青年研究人员奖支持与生物相关的无机化学的研究。该项目的重点是阐明金属离子在重要的生物转化中的作用。特别令人感兴趣的是过渡金属离子参与细胞色素氧化酶还原氧气的末端步骤和光合作用装置释放氧气的过程。这些金属蛋白和其他金属蛋白，特别是含锰蛋白的金属中心的小分子类似物将被合成和表征。一般的策略包括有机配体的设计和合成，它们与过渡金属的配合物的制备和纯化，以及通过各种结构、磁性和光谱技术对这种体系进行彻底的表征。除上述体系外，其他感兴趣的体系还包括亚硫酸盐还原酶中磁性偶联的铁血红素和二铁-硫簇，以及镍参与氢酶和产甲烷活性。最后，探讨了低价钒在氮气转化为氨和联氨反应中的作用。对模型化合物的光谱和化学性质的比较有望对模拟的生物系统的详细工作原理产生有价值的见解。

This Presidential Young Investigator Award from the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research in biologically relevant inorganic chemistry. The emphasis of the project is the elucidation of the role of metal ions in important biological transformations. Of particular interest is the participation of transition metal ions in the terminal steps of the reduction of dioxygen by cytochrome oxidase and the evolution of oxygen by the photosynthetic apparatus. Small molecule analogs of the metal centers of these and other metalloproteins, especially manganese-containing proteins, will be synthesized and characterized. The general strategy involves the design and synthesis of organic ligands, preparation and purification of their complexes with transition metals, and thorough characterization of such systems by a variety of structural, magnetic, and spectroscopic techniques. In addition to the systems mentioned above, others of interest include the magnetically-coupled siroheme and diron-sulfur cluster in sulfite reductase, and the participaton of nickel in hydrogenase and methanogenesis activity. Finally, the role of low valent vanadium in catalyzing the conversion of dinitrogen to ammonia and hydrazine will be explored. Comparison of the spectroscopic and chemical properties of the model compounds is expected to yield valuable insight into the detailed workings of the modeled biological systems.