Insight into the Iron-Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands.
Insight into the Iron-Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands.
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DOI：
10.1021/jacs.6b00747
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发表时间：
2016-06-15
影响因子：
15
通讯作者：
Holland PL
中科院分区：
文献类型：
--
作者：
Čorić I;Holland PL
固氮酶被微生物用于将大气中的N2转化为氨，氨为高等生物提供了氮原子的重要来源。依赖于氘的固氮酶的活性位点是独特的含碳化物的铁硫簇，称为铁钼辅因子（FeMoco）。在FeMoco上，N2结合被认为发生在一个或多个铁原子上，但催化中间体的结构尚不清楚。为了确定生物N2还原过程中不同潜在机制步骤的可行性，化学家们制备了模拟FeMoco中铁位点的各种结构方面的铁络合物。这种还原论方法提供了机械的见解，也揭示了可以更广泛地用于小分子活化的基本原理。在这里，我们回顾了最近的结果，并强调了未来研究的方向。在一个方向上，合成的铁络合物现在已经显示出结合N2，破坏N-N三键，并催化产生氨。碳和硫基供体已被纳入Fe-N2配合物的配体球，以显示这些原子如何影响FeMoco的结构和反应性。氢化物已被并入合成系统中，其可以结合N2，还原一些固氮酶底物，和/或还原性地消除H2以产生还原的铁中心。虽然已知一些含碳化物的铁簇，但还没有一个像FeMoco那样具有硫化物桥或高自旋铁原子。
Nitrogenase enzymes are used by microorganisms for converting atmospheric N2 to ammonia, which provides an essential source of N atoms for higher organisms. The active site of the molybdenum-dependent nitrogenase is the unique carbide-containing iron-sulfur cluster called the iron-molybdenum cofactor (FeMoco). On the FeMoco, N2 binding is suggested to occur at one or more iron atoms, but the structures of the catalytic intermediates are not clear. In order to establish the feasibility of different potential mechanistic steps during biological N2 reduction, chemists have prepared iron complexes that mimic various structural aspects of the iron sites in FeMoco. This reductionist approach gives mechanistic insight, and also uncovers fundamental principles that could be used more broadly for small molecule activation. Here, we review recent results and highlight directions for future research. In one direction, synthetic iron complexes have now been shown to bind N2, break the N-N triple bond, and produce ammonia catalytically. Carbon and sulfur based donors have been incorporated into the ligand spheres of Fe-N2 complexes to show how these atoms may influence the structure and reactivity of the FeMoco. Hydrides have been incorporated into synthetic systems, which can bind N2, reduce some nitrogenase substrates, and/or reductively eliminate H2 to generate reduced iron centers. Though some carbide-containing iron clusters are known, none yet have sulfide bridges or high-spin iron atoms like the FeMoco.
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