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硫酯桥联Fe(IV)Fe(IV)μ-氮化络合物及其对氨生成的加氢反应
作者:小柯机器人 发布时间:2021/12/26 12:49:11

大连理工大学Jingping Qu研究团队近日合成了一种硫酯桥联FeIVFeIV μ-氮化络合物,并研究了其对氨生成的加氢反应。该项研究成果发表在2021年12月23日出版的《自然-化学》上。

在该文中,研究人员报道了一个结构明确的硫酯桥接FeIVFeIV μ-氮化络合物,具有一个罕见的弯曲Fe-N-Fe部分。值得注意的是,该配合物在常温条件下表现出良好的加氢活性,能以较高的产率形成氨。结合实验和计算研究表明,硫酯桥接的FeIIIFeIII μ-酰胺配合物是一个关键中间体,它是通过一种少见的H2两电子氧化生成的。此外,以水作为质子来源、用电子处理该二铁μ-氮化物也可实现氨的生成。

据介绍,氮化铁是生物固氮和工业Haber-Bosch过程的关键中间体,被用于将N2转化为氨。然而,将氮化物逐步转化为氨的方式仍然是不确定的。有鉴于此,寻找明确的的多铁氮化物模型配合物以及控制其对氨生成反应性的研究既重要又富有挑战性。

附:英文原文

Title: A thiolate-bridged FeIVFeIV μ-nitrido complex and its hydrogenation reactivity toward ammonia formation

Author: Zhang, Yixin, Zhao, Jinfeng, Yang, Dawei, Wang, Baomin, Zhou, Yuhan, Wang, Junhu, Chen, Hui, Mei, Tao, Ye, Shengfa, Qu, Jingping

Issue&Volume: 2021-12-23

Abstract: Iron nitrides are key intermediates in biological nitrogen fixation and the industrial Haber–Bosch process, used to form ammonia from dinitrogen. However, the proposed successive conversion of nitride to ammonia remains elusive. In this regard, the search for well-described multi-iron nitrido model complexes and investigations on controlling their reactivity towards ammonia formation have long been of great challenge and importance. Here we report a well-defined thiolate-bridged FeIVFeIV μ-nitrido complex featuring an uncommon bent Fe–N–Fe moiety. Remarkably, this complex shows excellent reactivity toward hydrogenation with H2 at ambient conditions, forming ammonia in high yield. Combined experimental and computational studies demonstrate that a thiolate-bridged FeIIIFeIII μ-amido complex is a key intermediate, which is generated through an unusual two-electron oxidation of H2. Moreover, ammonia production was also realized by treating this diiron μ-nitride with electrons and water as a proton source.

DOI: 10.1038/s41557-021-00852-6

Source: https://www.nature.com/articles/s41557-021-00852-6

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex