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Oxidatively Induced C-H Activation at High Valent Nickel

机译:高价镍的氧化诱导C-H活化

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摘要

This communication describes a series of oxidatively induced intramolecular arene C-H activation reactions of Ni~(II) model complexes to yield Ni~(IV) σ-aryl products. These reactions proceed within 10 min at room temperature, which represents among the mildest conditions reported for C-H cleavage at a Ni center. A combination of density functional theory and preliminary experimental mechanistic studies implicate a pathway involving initial 2e~ oxidation of the Ni~(II) starting materials by the F~+ transfer reagent N-fluoro-2,4,6-trimethylpyr-idinium triflate followed by triflate-assisted C-H cleavage at Ni~(IV) to yield the products.
机译:该交流描述了Ni〜(II)模型配合物的一系列氧化诱导的分子内芳烃C-H活化反应,以生成Ni〜(IV)σ-芳基产物。这些反应在室温下进行10分钟之内,这代表了Ni中心发生C-H裂解的最温和条件。密度泛函理论和初步的实验机理研究相结合,暗示了一条途径,涉及到F +转移试剂N-氟-2,4,6-三甲基吡啶-三氟甲磺酸钠随后对Ni〜(II)原料进行初始2e〜氧化。用三氟甲磺酸盐辅助的Ni〜(IV)裂解CH生成产物。

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  • 来源
    《Journal of the American Chemical Society》 |2017年第17期|6058-6061|共4页
  • 作者单位

    Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, Michigan 48109, United States;

    Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, Michigan 48109, United States;

    School of Physical Sciences, University of Tasmania, Hobart, Tasmania 7001, Australia;

    School of Physical Sciences, University of Tasmania, Hobart, Tasmania 7001, Australia;

    Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, Michigan 48109, 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
  • 中图分类
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  • 入库时间 2022-08-18 03:07:57

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