Models for Iron Active Sites of Nitrogenases

描述(申请人提供)：将生成与固氮酶相关的生物启发功能铁模型络合物，重点是氮素的激活。将分离Chatt型循环中的关键还原氮中间体，并检查这些化合物的物理和光谱性质。氮化铁、氮烯、二叠氮基、酰肼、氨基和胺官能团的基本物理性质是人们所需要的。首先，我们将研究一系列强场配体。这些配体的低价铁配合物能够激活氮，但随后的反应活性尚未被探索。特别令人感兴趣的是铁(IV)氮化物，因为它们适用于基团转移过程。将进行一些光谱研究，以详细描述这些独特中间体的电子结构。将通过动力学和光谱方法研究金属-氮化物中间体的形成和衰变机理。在下一阶段，将考察富硫配体，并考察将其应用于基团转移过程的可能性。通过这些仿生复合体获得的氮活化原理，将更好地理解铁在固氮酶中的作用。

DESCRIPTION (provided by applicant): Bioinspired functional iron model complexes related to nitrogenase will be generated focusing on the activation of dinitrogen. Key reduced nitrogen intermediates in a Chatt-type cycle will be isolated and the physical and spectroscopic properties of these compounds examined. The basic physical properties of iron nitrides, nitrenes, diazenidos, hydrazido, amido and amine functionalities are desired. Initially a series of strong field ligands will be examined. Low valent iron complexes of these ligands are capable of activating dinitrogen, but the subsequent reactivity has not been explored. Of particular interest are iron (IV)-nitrides for their applicability to group transfer processes. A number of spectroscopic studies will be undertaken to detail the electronic structures of these unique intermediates. The mechanism of formation and decay of metal-dinitrogen intermediates will be studied via kinetic and spectroscopic methods. In the next phase, sulfur rich ligands will be examined and the possibility of the application to group transfer processes will be examined. Through the principles of nitrogen activation gained from these biomimetic complexes, greater understanding of the role of iron in nitrogenase will be gained.