日本京都大学Ohki, Yasuhiro团队报道了用合成的[Mo3S4Fe]立方体的Fe位还原氮。相关研究成果发表在2022年7月6日出版的《自然》。
由固氮酶进行的自然固氮是提供生物有效态氮的关键过程。这种酶使用一种独特的过渡金属-硫-碳簇作为其活性中心辅因子（[（R-高柠檬酸盐）MoFe7S9C]，FeMoco），并且假设硫包围的铁（Fe）原子能够捕获和还原N2。尽管有近50年的研究，虽然有一些FeMoco的合成对应物，即金属硫簇的例子，已经显示出N2的结合，但通过任何合成金属硫簇或FeMoco10的提取形式来还原N2仍然是难以捉摸的。
该文中，研究表明，研究人员合成的[Mo3S4Fe]立方体中的铁原子可以捕获N2分子，并在过量钠和三甲基硅酰氯处理下催化N2硅烷化形成N（SiMe3）3。这些结果举例说明了合成金属-硫簇对N2的催化硅烷化，并证明了铁原子在富硫环境中的N2还原能力，这让人想起FeMoco结合和激活N2的能力。
附：英文原文
Title: Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes
Author: Ohki, Yasuhiro, Munakata, Kenichiro, Matsuoka, Yuto, Hara, Ryota, Kachi, Mami, Uchida, Keisuke, Tada, Mizuki, Cramer, Roger E., Sameera, W. M. C., Takayama, Tsutomu, Sakai, Yoichi, Kuriyama, Shogo, Nishibayashi, Yoshiaki, Tanifuji, Kazuki
Issue&Volume: 2022-07-06
Abstract: Nitrogen (N2) fixation by nature, which is a crucial process for the supply of bio-available forms of nitrogen, is performed by nitrogenase. This enzyme uses a unique transition-metal–sulfur–carbon cluster as its active-site co-factor ([(R-homocitrate)MoFe7S9C], FeMoco)1,2, and the sulfur-surrounded iron (Fe) atoms have been postulated to capture and reduce N2 (refs. 3,4,5,6). Although there are a few examples of synthetic counterparts of the FeMoco, metal–sulfur cluster, which have shown binding of N2 (refs. 7,8,9), the reduction of N2 by any synthetic metal–sulfur cluster or by the extracted form of FeMoco10 has remained elusive, despite nearly 50years of research. Here we show that the Fe atoms in our synthetic [Mo3S4Fe] cubes11,12 can capture a N2 molecule and catalyse N2 silylation to form N(SiMe3)3 under treatment with excess sodium and trimethylsilyl chloride. These results exemplify the catalytic silylation of N2 by a synthetic metal–sulfur cluster and demonstrate the N2-reduction capability of Fe atoms in a sulfur-rich environment, which is reminiscent of the ability of FeMoco to bind and activate N2.
DOI: 10.1038/s41586-022-04848-1
Source: https://www.nature.com/articles/s41586-022-04848-1