Reduction of C1 Substrates to Hydrocarbons by the Homometallic Precursor and Synthetic Mimic of the Nitrogenase Cofactor

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• 作者：Nathaniel S. Sickerman ; Kazuki TanifujiChi Chung Lee ; Yasuhiro Ohki ; Kazuyuki Tatsumi ; Markus W. Ribbe ; Yilin Hu
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 18, 2017
• 年：2017
• 卷：139
• 期：2
• 页码：603-606
• 全文大小：363K
• ISSN：1520-5126

文摘

Solvent-extracted nitrogenase cofactors can reduce C₁ substrates (CN^–, CO and CO₂) to hydrocarbons in reactions driven by a strong reductant, SmI₂ (E^0′ = −1.55 V vs SCE). Here we show that a synthetic [Et₄N]₄[Fe₆S₉(SEt)₂] cluster (designated the Fe₆^RHH-cluster), which mimics the homometallic [Fe₈S₉C] core of the nitrogenase cofactor (designated the L-cluster), is capable of conversion of C₁ substrates into hydrocarbons in the same reactions. Comparison of the yields and product profiles between these homometallic clusters and their heterometallic counterparts points to possible roles of the heterometal, interstitial carbide and belt sulfur-bridged iron atoms in catalysis. More importantly, the observation that a “simplified”, homometallic cofactor mimic can perform Fischer–Tropsch-like hydrocarbon synthesis suggests future biotechnological adaptability of nitrogenase-based biomimetic compounds for recycling C₁ substrates into useful chemical and fuel products.