Chemical Synthesis of an Asymmetric Mo-Fe-S Mimic of Nitrogenase Active Site
Chemical Synthesis of an Asymmetric Mo-Fe-S Mimic of Nitrogenase Active Site
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固氮酶活性位点不对称 Mo-Fe-S 模拟物的化学合成
DOI：
10.1007/978-1-4939-8864-8_15
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
Yasuhiro Ohki
中科院分区：
文献类型：
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作者：
Kazuki Tanifuji;Yasuhiro Ohki
金属-硫（M- s, M = metals）簇的合成无机化学对氮酶的生化分析起到了重要的补充作用，有助于更好地了解酶的活性位点。以溶剂稳定的形式[(cit)MoFe7S9C] （cit = (R)-homocitrate）从蛋白质中提取出氮酶的活性位点（指定为m簇）。提取的m簇的一个重要发现是它对c1 -底物（CN−，CO, CO2）在溶液中还原成c1 - c5碳氢化合物的催化活性。这种催化性质给化学家们提出了用合成模拟物再现其功能的挑战，这不仅是因为生物化学方面的兴趣，还因为它在绿色化学和催化研究中的潜在意义。在此背景下，我们成功合成了不对称Mo-Fe-S簇[Cp*MoFe5S9(SH)]3−，这是合成M-S化学的最新重要成果之一，因为该簇以与提取的m -簇相似的方式催化c1底物的还原。尽管该簇的合成方案已在文献中描述，但对于不熟悉合成M-S化学的研究人员来说，仍有许多陷阱。在本章中，我们提供了合成[Cp*MoFe5S9(SH)]3−的一般注意事项和详细的方案，并根据作者在生化和合成化学领域的经验简要讨论了实验技巧。
The synthetic inorganic chemistry of metal–sulfur (M-S, M = metals) clusters has played an important, complementary role to the biochemical analyses of nitrogenase toward a better understanding of the enzyme active site. The active site of nitrogenase (designated the M-cluster) can be extracted from the protein in a solvent-stabilized form, [(cit)MoFe7S9C] (cit = (R)-homocitrate). One important finding of the extracted M-cluster is its catalytic activity toward the reduction of C1-substrates (CN−, CO, CO2) into C1–C5hydrocarbons in solution. This catalytic property poses challenges for chemists to reproduce the function with synthetic mimics, not only because of the biochemical interests but also due to the potential significance in green chemistry and catalysis research. In this context, our successful synthesis of an asymmetric Mo-Fe-S cluster, [Cp*MoFe5S9(SH)]3−, is one of the recent important achievements in synthetic M-S chemistry, as this cluster catalyzes the reduction of C1-substrates in a similar manner to the extracted M-cluster. Even though the synthetic protocol for this cluster has been described in the literature, there are plenty of pitfalls for researchers unfamiliar with synthetic M-S chemistry. In this chapter, we provide general precautionary statements and detailed protocols for the synthesis of [Cp*MoFe5S9(SH)]3−, with a brief discussion of the experimental tips based on the authors’ experience in both biochemical and synthetic chemical fields.