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通过串联催化升级轻烃:用于烷烃/烯烃偶联的双均相 Ta/Ir 体系。

Upgrading light hydrocarbons via tandem catalysis: a dual homogeneous Ta/Ir system for alkane/alkene coupling.

机构信息

Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, United States.

出版信息

J Am Chem Soc. 2013 Jul 17;135(28):10302-5. doi: 10.1021/ja405191a. Epub 2013 Jul 2.

Abstract

Light alkanes and alkenes are abundant but are underutilized as energy carriers because of their high volatility and low energy density. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel molecules. This process involves alkane dehydrogenation by a pincer-ligated iridium complex and alkene dimerization by a Cp*TaCl2(alkene) catalyst. These two homogeneous catalysts operate with up to 60/30 cooperative turnovers (Ir/Ta) in the dimerization of 1-hexene/n-heptane, giving C13/C14 products in 40% yield. This dual system can also effect the catalytic dimerization of n-heptane (neohexene as the H2 acceptor) with cooperative turnover numbers of 22/3 (Ir/Ta).

摘要

轻烷烃和烯烃虽然丰富,但由于其高挥发性和低能量密度,尚未得到充分利用作为能源载体。为了将这些低碳氢化合物升级为重质燃料分子,已经开发出一种串联催化方法来偶联烷烃和烯烃。该过程涉及通过钳形配体铱配合物进行烷烃脱氢和通过 Cp*TaCl2(烯烃)催化剂进行烯烃二聚化。这两种均相催化剂在 1-己烯/正庚烷的二聚化中以高达 60/30 的协同转化率(Ir/Ta)操作,在 40%的产率下得到 C13/C14 产物。该双体系还可以通过协同转化率 22/3(Ir/Ta)来催化正庚烷(作为 H2 接受体的新己烯)的催化二聚化。

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