Synthetic Routes to a Model of the Nitrogenase Cofactor

描述(由申请人提供)： 在充足的光照和水分存在下，植物生长的主要限制因素是生物有效氮和氨。工厂中的固氮是在环境条件下进行的，而工业生产氨需要如此密集的条件，以至于每年消耗的能源约占世界能源产量的1%。固氮酶的铁钼辅因子(FeMoco)是氮素还原为氨的部位。固氮酶活性中心的复杂结构由7个铁原子、1个钼原子和9个硫原子组成的双头三棱柱组成。最近，高分辨率单晶X射线结构显示，团簇核心中心有一个间隙原子，很可能是氮原子。这样的团簇在铁化学中是前所未有的。本文提出了一种合成电子结构类似于固氮酶辅助因子的氮化铁簇合物的合成路线，并提出了利用这些氮化铁簇合物作为骨架来构建类似辅因子的簇合物的合成方案。与固氮酶辅助因子的合成类似物有关的新的合成方法正在开发中。

DESCRIPTION (provided by applicant): In the presence of sufficient light and water the major limiting factor to plant growth is bioavailable nitrogen, ammonia. Nitrogen fixation in plants occurs under ambient conditions while industrial production of ammonia requires conditions so energy intensive they consume approximately 1% of the world's energy production annually. The iron-molybdenum cofactor (FeMoco) of the nitrogenase enzyme is the site of dinitrogen reduction to ammonia. The complex structure of the active site of nitrogenase comprises a bicapped trigonal prism of seven iron atoms, one molybdenum atom, and nine sulfur atoms. Recently, a high-resolution single crystal X-ray structure revealed an interstitial atom at the center of the cluster core which is most likely a nitrogen atom. Such a cluster was unprecedented in iron chemistry. Herein, a synthetic route to iron-nitride clusters with electronic structures similar to the cofactor of the nitrogenase is presented, and synthetic schemes utilizing these ferric-nitride clusters as scaffolds for the construction of a cluster similar to the cofactor are proposed. New synthetic methodologies relevant to synthetic analogues of the cofactor of nitrogenase are being developed.