Department of Systems Innovation, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-8656, Japan.
Institute for Materials Chemistry and Engineering and International Research Center for Molecular System, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan.
Nat Commun. 2016 Jul 20;7:12181. doi: 10.1038/ncomms12181.
Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase.
铁-氮配合物的合成和反应性已得到广泛研究，因为铁原子在工业和生物固氮中起着重要作用。因此，最近已经实现了铁催化将分子氮还原为氨。在这里，我们展示了一种带有阴离子 PNP 钳形配体的铁-氮配合物可作为有效的催化剂，用于催化氮的固定，其中生成氨和联氨的混合物。在本反应体系中，通过使用过渡金属-氮配合物作为催化剂，将分子氮催化直接转化为联氨。因为联氨被认为是固氮酶中固氮的关键中间体，所以本文所描述的发现为阐明固氮酶中的反应机制提供了机会。
