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Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

机译：一氧化碳在单个金属位点的四电子脱氧还原偶联

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摘要

Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained(1). Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide(2), further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging(3). Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources(4). Electrocatalytic reduction of carbon monoxide on copper catalysts(5) also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures(6). However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively(6-23) to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand(24,25), which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for converting carbon monoxide to chemical fuels, and should prove useful in the broader context of performing complex multi-electron transformations at a single metal site.
机译：二氧化碳是化石燃料的终极来源，而化石燃料对于现代生活来说是至关重要的，而且也是有问题的：二氧化碳的使用会增加大气中温室气体的含量，并且其可用性受到地缘政治限制（1）。原则上，使用二氧化碳作为原料生产合成燃料可以减轻这些担忧。尽管许多均相和非均相催化剂将二氧化碳转化为一氧化碳（2），但一氧化碳的进一步脱氧偶联以生成有用的多碳产物仍然具有挑战性（3）。钼和钒的固氮酶能够在温和的条件下使用离散的电子和质子源将一氧化碳转化为碳氢化合物（4）。一氧化碳在铜催化剂上的电催化还原（5）也使用电子和质子的组合，而工业费-托工艺使用二氢作为电子和亲电子的组合来源，以在高温和高压下进行一氧化碳的偶联（6）。但是，这些酶和异构系统很难用机械方法探测。分子催化剂已被广泛研究（6-23），以研究一氧化碳脱氧和偶联的基本步骤，但能够有效诱导所需的碳-氧键断裂并生成碳-碳键的单个金属位点尚未实现尚未记录。在这里，我们描述了一种由三联苯-二膦配体支撑的钼化合物，该化合物激活并裂解一氧化碳的强碳-氧键，进行碳-碳偶联，并自发解离所得片段。叔苯基-二膦配体（24,25）使这种复杂的四电子转化成为可能，该配体充当电子库并显示出稳定整个反应序列中涉及的不同中间体所需的配位柔性。我们预计，这些设计元素可能有助于开发将一氧化碳转化为化学燃料的高效催化剂，并应证明在更广泛的背景下在单个金属位点进行复杂的多电子转化非常有用。

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  • 来源
    《Nature》 |2016年第7584期|72-75|共4页
  • 作者

    Buss Joshua A.; Agapie Theodor;

  • 作者单位

    CALTECH, Div Chem & Chem Engn, 1200 East Calif Blvd,MC 127-72, Pasadena, CA 91125 USA;

    CALTECH, Div Chem & Chem Engn, 1200 East Calif Blvd,MC 127-72, Pasadena, CA 91125 USA;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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  • 正文语种 eng
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