首页> 外文期刊>Journal of the American Chemical Society >β-Hydride Elimination and C-H Activation by an Iridium Acetate Complex, Catalyzed by Lewis Acids. Alkane Dehydrogenation Cocatalyzed by Lewis Acids and [2,6-Bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl]iridium
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β-Hydride Elimination and C-H Activation by an Iridium Acetate Complex, Catalyzed by Lewis Acids. Alkane Dehydrogenation Cocatalyzed by Lewis Acids and [2,6-Bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl]iridium

机译:路易斯酸催化的乙酸铱络合物消除β-氢化物和C-H活化。路易斯酸和[2,6-双(4,4-二甲基恶唑啉基)-3,5-二甲基苯基]铱共同催化的烷烃脱氢

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摘要

NaBAr_4~F (sodium tetrakis[(3,5-trifluoromethyl)-phenyl]borate) was found to catalyze reactions of (Phebox)lr~(III)-(acetate) (Phebox = 2,6-bis(4,4-dimethyIoxazolinyl)-3,5-dime-thylphenyl) complexes, including (i) β-H elimination of (Phebox)Ir(OAc)(n-alkyl) to give (Phebox)Ir(OAc)(H) and the microscopic reverse, alkene insertion into the Ir-H bond of (Phebox)Ir(OAc)(H), and (ii) hydrogenolysis of the Ir-alkyl bond of (Phebox)Ir(OAc)(n-alkyl) and the microscopic reverse, C-H activation by (Phebox)Ir(OAc)(H), as indicated by H/D exchange experiments. For example, β-H elimination of (Phebox)lr(OAc)(n-octyl) (2-Oc) proceeded on a time scale of minutes at -15 ℃ in the presence of (0.4 mM) NaBAr_4~F as compared with a very slow reaction at 125 °C in the absence of NaBAr_4~F. In addition to NaBAr_4~F, other Lewis acids are also effective. Density functional theory calculations capture the effect of the Na~+ cation and indicate that it operates primarily by promoting k~2-k~1 dechelation of the acetate anion, which opens the coordination site needed to allow the observed reaction to proceed. In accord with the effect on these individual stoichiometric reactions, NaBAr_4~F was also found to cocatalyze, with (Phebox)Ir(OAc)(H), the acceptorless dehydrogenation of n-dodecane.
机译:发现NaBAr_4〜F(四[(3,5-三氟甲基)-苯基]硼酸钠)催化(Phebox)lr〜(III)-(乙酸)(Phebox = 2,6-bis(4,4-二甲基恶唑啉基)-3,5-二甲硫基苯基)配合物,包括(i)β-H消除(Phebox)Ir(OAc)(n-烷基)生成(Phebox)Ir(OAc)(H)和微观反转,将烯烃插入(Phebox)Ir(OAc)(H)的Ir-H键中,以及(ii)(Phebox)Ir(OAc)(n-烷基)的Ir-烷基键氢解和微观相反的结果, H / D交换实验表明,通过(Phebox)Ir(OAc)(H)激活CH。例如,在(0.4 mM)NaBAr_4〜F存在的条件下,在-15℃下以几分钟的时间规模进行(Phebox)lr(OAc)(n-辛基)(2-Oc)的β-H消除。在没有NaBAr_4〜F的情况下,在125°C下反应非常缓慢。除NaBAr_4〜F外,其他路易斯酸也有效。密度泛函理论计算捕获了Na〜+阳离子的作用,并表明它主要通过促进乙酸根阴离子的k〜2-k〜1脱螯作用而打开,从而打开了允许观察到的反应进行的配位点。与对这些单独的化学计量反应的影响相一致,还发现NaBAr_4〜F与(Phebox)Ir(OAc)(H)共同催化正十二烷的无受体脱氢。

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  • 来源
    《Journal of the American Chemical Society》 |2017年第18期|6338-6350|共13页
  • 作者单位

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States,Department of Natural Sciences, Lawrence Technological University, Southfield, Michigan 48075, United States;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States,Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States;

    Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States;

    Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States;

    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States;

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  • 入库时间 2022-08-18 03:07:58

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