Mackinawite‐Supported Reduction of C 1 Substrates into Prebiotically Relevant Precursors
Mackinawite‐Supported Reduction of C 1 Substrates into Prebiotically Relevant Precursors
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Mackinawite — 支持将 C 1 底物还原为益生元相关前体
DOI：
10.1002/syst.202200010
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Ribbe, Markus
中科院分区：
文献类型：
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作者：
Grosch, Mario;Stiebritz, Martin T.;Bolney, Robert;Winkler, Mario;Jückstock, Eric;Busch, Hannah;Peters, Sophia;Siegle, Alexander F.;van Slageren, Joris;Ribbe, Markus
与其他铁硫化物相比，麦基诺石具有独特的结构性质和反应性。在此，我们提供了在原始条件下mackinawite支持的KCN还原成各种还原化合物的证据。我们提出了一种反应机理，该反应机理基于脱质子化的mackinawite-SH表面基团在HCN的碳原子上的亲核攻击。通过DFT计算和使用其他底物（如KSCN、KOCN和CS2）的进一步实验，支持底物的初始结合和随后的还原事件。到目前为止，CN−转化为CH 4和NH3仅限于固氮酶辅因子或分子Fe-CN复合物。我们的研究为在环境条件下mackinawite支持的C-N键断裂提供了证据，这为研究mackinawite支持的反应的其他底物开辟了新的途径，同时揭示了这种类型的反应与地球生命起源的相关性。
Mackinawite has unique structural properties and reactivities when compared to other iron sulfides. Herein we provide evidence for the mackinawite‐supported reduction of KCN into various reduced compounds under primordial conditions. We proposed a reaction mechanism based on the nucleophilic attack by the deprotonated mackinawite ‐SH surface groups at the carbon atom of HCN. The initial binding of the substrate and the subsequent reduction events are supported by DFT calculations and further experiments using other substrates, such as KSCN, KOCN and CS2. Until now, conversion of CN−into CH4and NH3has been limited to nitrogenase cofactors or molecular Fe‐CN complexes. Our study provides evidence for mackinawite‐supported cleavage of the C−N bond under ambient conditions, which opens new avenues for investigation of other substrates for mackinawite‐supported reactions while shedding light on the relevance of this type of reaction to the origin of life on Earth.