Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes
Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes
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DOI：
10.1038/s41586-022-04848-1
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发表时间：
2022-07-07
期刊：
影响因子：
64.8
通讯作者：
Tanifuji, Kazuki
中科院分区：
文献类型：
--
作者：
Ohki, Yasuhiro;Munakata, Kenichiro;Tanifuji, Kazuki
自然界的氮（N-2）固定是供给生物可利用形式氮的关键过程，由固氮酶完成。该酶使用一种独特的过渡金属-硫-碳簇作为其活性位点辅助因子（[(R-homocitrate)MoFe7S9C], FeMoco）（1,2），并且硫包围的铁（Fe）原子被假设捕获和还原N-2（参考文献（3-6））。虽然有一些FeMoco的合成对应物的例子，但金属-硫簇已经显示出N-2的结合（参考文献）。（7-9）)，尽管近50年的研究，任何合成的金属硫簇或提取形式的FeMoco（10）对N-2的还原仍然是难以捉摸的。本研究表明，在过量钠和三甲基硅酰氯的作用下，我们合成的[Mo3S4Fe]立方体（11,12）中的铁原子可以捕获N-2分子并催化N-2硅基化生成N(SiMe3)(3)。这些结果证明了合成金属硫簇催化N-2的硅基化，并证明了铁原子在富硫环境中还原N-2的能力，这让人想起了FeMoco结合和激活N-2的能力。
Nitrogen (N-2) 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 N-2 (refs.(3-6)). Although there are a few examples of synthetic counterparts of the FeMoco, metal-sulfur cluster, which have shown binding of N-2 (refs.(7-9)), the reduction of N-2 by any synthetic metal-sulfur cluster or by the extracted form of FeMoco(10) has remained elusive, despite nearly 50 years of research. Here we show that the Fe atoms in our synthetic [Mo3S4Fe] cubes(11,12) can capture a N-2 molecule and catalyse N-2 silylation to form N(SiMe3)(3) under treatment with excess sodium and trimethylsilyl chloride. These results exemplify the catalytic silylation of N-2 by a synthetic metal-sulfur cluster and demonstrate the N-2-reduction capability of Fe atoms in a sulfur-rich environment, which is reminiscent of the ability of FeMoco to bind and activate N-2.