Models for Iron Active Sites of Nitrogenases

描述（由申请人提供）：将生成与固氮酶相关的生物启发功能性铁模型复合物，重点关注二氮的活化。在查特型循环中的关键还原氮中间体将被分离，并检查这些化合物的物理和光谱性质。需要铁氮化物、氮烯、二氮烯、肼基、酰氨基和胺官能团的基本物理性质。首先将研究一系列强场配体。这些配体的低价铁络合物能够活化二氮，但随后的反应性尚未探索。特别感兴趣的是铁（IV）-氮化物，因为它们适用于基团转移过程。一些光谱研究将进行详细的电子结构，这些独特的中间体。将通过动力学和光谱方法研究金属-二氮中间体的形成和衰变机制。在下一阶段中，富硫配体将被检查，并将检查应用于基团转移过程的可能性。通过这些仿生配合物的氮激活原理，将获得更多的了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.