High-Efficiency Reduction of C1 Substrates to Hydrocarbons by the Homometallic Precursor and Synthetic Mimic of the Nitrogenase Cofactor
High-Efficiency Reduction of C1 Substrates to Hydrocarbons by the Homometallic Precursor and Synthetic Mimic of the Nitrogenase Cofactor
复制标题
通过固氮酶辅因子的同金属前体和合成模拟物高效地将 C1 底物还原为碳氢化合物
DOI：
10.1021/jacs.6b11633
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发表时间：
2017
影响因子：
15
通讯作者：
Yilin Hu
中科院分区：
文献类型：
--
作者：
Nathaniel S. Sickerman;Kazuki Tanifuji;Yasuhiro Ohki;Kazuyuki Tatsumi;Markus W. Ribbe;Yilin Hu
溶剂萃取的固氮酶辅因子可以在强还原剂SmI 2（E0′= −1.55 V vs SCE）驱动的反应中将C1底物（CN-、CO和CO2）还原为碳氢化合物。在这里，我们表明，一个合成的[Et 4 N]4[Fe 6S 9（SEt）2]簇（指定的Fe 6 RHH-簇），它模仿的homomorphic [Fe 8 S9 C]核心的固氮酶辅因子（指定的L-簇），是能够转换C1底物在相同的反应成烃。这些homophores集群和它们的异金属对应物之间的产量和产品配置文件的比较点的异金属，间隙碳化物和带硫桥连的铁原子在催化中的可能作用。更重要的是，观察到一个“简化”，homeplasticcofactor模拟可以进行费托合成类似的碳氢化合物表明未来的生物技术的适应性固氮酶为基础的仿生化合物回收C1底物到有用的化学和燃料产品。
Solvent-extracted nitrogenase cofactors can reduce C1substrates (CN–, CO and CO2) to hydrocarbons in reactions driven by a strong reductant, SmI2(E0′= −1.55 V vs SCE). Here we show that a synthetic [Et4N]4[Fe6S9(SEt)2] cluster (designated the Fe6RHH-cluster), which mimics the homometallic [Fe8S9C] core of the nitrogenase cofactor (designated the L-cluster), is capable of conversion of C1substrates 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 C1substrates into useful chemical and fuel products.