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首页> 外文期刊>RSC Advances >Direct coupling of unactivated alkynes and C(sp(3))-H bonds catalyzed by a Pt(II, IV)-centered catalyst: a computational study
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Direct coupling of unactivated alkynes and C(sp(3))-H bonds catalyzed by a Pt(II, IV)-centered catalyst: a computational study

机译：通过PT（II，IV） - CONCEDTED催化剂催化的未活化炔烃和C（SP（3）） - H键的直接耦合：计算研究

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摘要

Direct coupling of unactivated alkynes and C(sp(3))-H bonds catalyzed by a Pt(II, IV)-centered catalyst X (X = PtCl2, PtBr2, PtI2 and PtI4) (J. Am. Chem. Soc. 2009, 131, 16525) have been theoretically investigated with density functional theory (DFT). A comprehensive mechanistic DFT study of these reactions was carried out to better understand the experimental outcomes, and divergent and substrate-/catalyst-dependent mechanisms for the formation of ether derivatives were uncovered based on the computational results. Free energy diagrams for three types of mechanisms were computed, (a) in Mechanism I, the transition state implies a directed 1,5-hydrogen shift (pathways a1-a4), (b) Mechanism II leads to the formation of a Pt(II, IV) vinyl carbenoid (pathway b), and (c) Mechanism III involves an O-coordinated Pt and includes 5,6-hydrogen migration (pathway c). Results suggest that the catalytic mechanism with PtI4 is different to PtCl2, PtBr2 and PtI2 catalysts. When PtCl2, PtBr2 and PtI2 were used the insertion reaction pathway a2 is favored while PtI4 adopted the pathway a1. Comparing the energy profiles, the pathway a1 with PtI4 is the most favored. Through 1,5-hydrogen transfer, the concerted insertion pathway a1 with carbocationic intermediate is favored while the vinyl carbenoid mechanism is implausible.
机译：通过Pt（II，IV） - 中心催化剂X（X = PTCL2，PTI2，PTI2和PTI4）催化的未活化炔烃和C（SP（3）） - H键的直接耦合（SP（3）） - H键（J.IM。化学。Soc。2009 ，131,16525）理论上已经用密度泛函理论（DFT）研究。对这些反应的综合机械DFT研究进行了以更好地了解实验结果，并且基于计算结果揭示了形成醚衍生物的发散和基底/催化剂依赖性机制。计算三种机构的自由能量图，（a）在机制I中，过渡状态意味着一个定向的1,5-氢变换（途径A1-A4），（B）机制II导致形成PT的形成（ II，IV）乙烯基羧酸（途径B）和（C）机制III涉及O-协调的PT，包括5,6-氢迁移（途径C）。结果表明，具有PTI4的催化机制与PTCl2，PTBR2和PTI2催化剂不同。当使用PTCL2，PTBR2和PTI2时，在PTI4采用途径A1时，粘连反应途径A2受到青睐。比较能量型材，具有PTI4的途径A1最有利。通过1,5-氢转移，在乙烯基甲骨羧酸机制是难以置信的同时，齐齐欲的插入途径A1有利于携带碳粉盒中间体。

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  • 来源
    《RSC Advances》 |2015年第40期|共11页
  • 作者

    Li Zhi-Feng; Li Hui-Xue; Yang Xiao-Ping; Liu Xin-Wen; Zuo Guo-Fang; Zhao Cunyuan;

  • 作者单位

    Tianshui Normal Univ Coll Life Sci &

    Chem Key Lab New Mol Design &

    Funct Gansu Univ Tianshui 741001 Peoples R China;

    Tianshui Normal Univ Coll Life Sci &

    Chem Key Lab New Mol Design &

    Funct Gansu Univ Tianshui 741001 Peoples R China;

    Tianshui Normal Univ Coll Life Sci &

    Chem Key Lab New Mol Design &

    Funct Gansu Univ Tianshui 741001 Peoples R China;

    Tianshui Normal Univ Coll Life Sci &

    Chem Key Lab New Mol Design &

    Funct Gansu Univ Tianshui 741001 Peoples R China;

    Tianshui Normal Univ Coll Life Sci &

    Chem Key Lab New Mol Design &

    Funct Gansu Univ Tianshui 741001 Peoples R China;

    Sun Yat Sen Univ Sch Chem &

    Chem Engn Guangzhou 510275 Guangdong Peoples R China;

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