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Long-Range C-H Bond Activation by Rh~(Ⅲ)-Carboxylates

机译:Rh〜(Ⅲ)-羧酸盐对C-H键的远距离活化作用

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摘要

Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a Rh~Ⅲ ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectro-scopically upon addition of a pyridine base to provide a thermodynamic trap.
机译:通过协同金属化-去质子化(CMD)机制激活的传统C-H键涉及到C-H键的预配位,然后从内部碱基去质子化。本文报道的是与Rh〜Ⅲ离子相距6个键的未配位苄基C-H键的“亚芳基”活化。通过实验和DFT研究进行了研究,其机理是通过脱芳构二甲苯中间体进行的。加入吡啶碱以提供热力学陷阱后,在光谱上观察到该中间体。

著录项

  • 来源
    《Journal of the American Chemical Society》 |2014年第42期|14690-14693|共4页
  • 作者单位

    Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, United States;

    Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States;

    Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States;

    Nanoscale Materials Characterization Facility, Department of Materials Science and Engineering, University of Virginia, Charlottesville, Virginia 22904-4319, United States;

    Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States;

    Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, United States;

  • 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);
  • 原文格式 PDF
  • 正文语种 eng
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  • 入库时间 2022-08-18 03:11:17

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