Partial Deoxygenative CO Homocoupling by a Diiron Complex.
Partial Deoxygenative CO Homocoupling by a Diiron Complex.
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通过 Diiron 配合物进行部分脱氧 CO 自偶联。
DOI：
10.1002/anie.202308813
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Murray,LeslieJ
中科院分区：
文献类型：
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作者：
Singh,Devender;Knight,BrianJ;Catalano,VincentJ;García-Serres,Ricardo;Maurel,Vincent;Mouesca,Jean-Marie;Murray,LeslieJ
解决气候变化的一个途径是将二氧化碳转化为合成碳中性燃料。虽然二氧化碳到CO的转化在同质催化和多相催化中有先例，但CO与C - C键的脱氧偶联-如在液体燃料中-仍然具有挑战性。在这里，我们报道了两个CO分子通过双铁配合物的偶联。Fe2(CO)2L(2)还原得到[K(THF)5][Fe2(CO)2L](3)，经过硅基化生成Fe2(CO)(COSiMe3)L(4)。随后的C‐osime3键裂解和C=C键形成发生在还原4时，生成Fe2(μ‐CCO)L。基于DFT计算、Mössbauer和EPR光谱，该系列CO衍生配体介导与烯基二烯的弱交换相互作用，提供最小的j值，改变局部金属离子自旋态和耦合方案（铁与反铁磁性）。最后，5与KEt3BH或甲醇反应释放C2O2−配体，并保留二铁核
One route to address climate change is converting carbon dioxide to synthetic carbon‐neutral fuels. Whereas carbon dioxide to CO conversion has precedent in homo‐ and heterogeneous catalysis, deoxygenative coupling of CO to products with C−C bonds—as in liquid fuels—remains challenging. Here, we report coupling of two CO molecules by a diiron complex. Reduction of Fe2(CO)2L(2), whereL2−is a bis(β‐diketiminate) cyclophane, gives [K(THF)5][Fe2(CO)2L] (3), which undergoes silylation to Fe2(CO)(COSiMe3)L(4). Subsequent C‐OSiMe3bond cleavage and C=C bond formation occurs upon reduction of4, yielding Fe2(μ‐CCO)L. CO derived ligands in this series mediate weak exchange interactions with the ketenylidene affording the smallestJvalue, with changes to local metal ion spin states and coupling schemes (ferro‐ vs. antiferromagnetism) based on DFT calculations, Mössbauer and EPR spectroscopy. Finally, reaction of5with KEt3BH or methanol releases the C2O2−ligand with retention of the diiron core