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首页> 外文期刊>ACS catalysis >Side Arm Twist on Zn-Catalyzed Hydrosilylative Reduction of CO2 to Formate and Methanol Equivalents with High Selectivity and Activity
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Side Arm Twist on Zn-Catalyzed Hydrosilylative Reduction of CO2 to Formate and Methanol Equivalents with High Selectivity and Activity

机译：侧臂扭曲Zn催化的CO 2的氢化硅化物减少，甲酸和具有高选择性和活性的甲醇等同物

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摘要

Reductive hydrosilylation of CO2 by catalysts based on environmentally benign metals such as zinc still presents an unmet challenge in terms of catalyst selectivity and activity. Here we show that tetra-coordinated neutral zinc siloxide complexes supported by the beta-diketiminato ligand bearing a pendant amine arm exhibit unprecedentedly high catalytic activity toward the selective reduction of CO2 by a hydrosilane to silyl formate. More significantly, this zinc catalyst system can also effectively catalyze the subsequent reduction of silyl formate into methoxysilane in quantitative yield. To understand the mechanism of the CO2 hydrosilylation and the influence of the side arm, a series of catalytic active species (or intermediates), zinc hydrides, and formates, has been synthesized and structurally characterized; the relevant stoichiometric reactions and kinetic study were performed. DFT calculations were also carried out to determine the reaction profiles for the CO2 hydrosilylation and to explain the relative activity of the zinc catalysts employed in this study. This combined experimental and theoretical study gives insights into the critical effects of the pendant amine donor arm and the size of the alkyl group of the amine on the relative energetics of the species involved in the proposed catalytic cycle.
机译：基于环境良性金属的催化剂如锌等催化剂在催化剂的选择性和活性方面仍然存在未结核挑战的催化剂的还原氢化硅烷化。在这里，我们表明，携带侧胺臂的β-二酮氨基硅酸盐配体支持的Tetra协调中性锌硅氧化物配合物，其朝向甲硅烷基甲酸甲硅烷基选择性降低CO 2的前所未有的高催化活性。更重要的是，该锌催化剂体系还可以有效地催化在定量产率的甲氧基甲酸盐中的随后还原成甲氧基硅烷。为了理解CO2氢化硅烷化的机理和侧臂的影响，已经合成和结构表征了一系列催化活性物质（或中间体），氢化锌和甲酸酯;进行了相关的化学计量反应和动力学研究。还进行了DFT计算以确定CO 2氢化硅烷化的反应型材，并解释本研究中使用的锌催化剂的相对活性。这种组合的实验和理论研究介绍了悬浮胺供体臂的临界效果和胺的烷基的烷基的尺寸对所提出的催化循环所涉及的物种的相对能量。

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  • 来源
    《ACS catalysis》 |2018年第5期|共9页
  • 作者

    Feng Guoqin; Du Chongyang; Xiang Li; del Rosal Iker; Li Guangyu; Leng Xuebing; Chen Eugene Y. -X.; Maron Laurent; Chen Yaofeng;

  • 作者单位

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

    Univ Paul Sabatier CNRS LPCNO 135 Ave Rangueil F-31077 Toulouse France;

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

    Colorado State Univ Dept Chem Ft Collins CO 80523 USA;

    Univ Paul Sabatier CNRS LPCNO 135 Ave Rangueil F-31077 Toulouse France;

    Univ Chinese Acad Sci Shanghai Inst Organ Chem Chinese Acad Sci State Key Lab Organometall Chem Ctr Excellence Mo 345 Lingling Rd Shanghai 200032 Peoples R China;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 物理化学（理论化学）、化学物理学;
  • 关键词

    CO2 reduction; DFT; hydrosilylation; zinc catalyst; pendant donor;

    机译：二氧化碳减少;DFT;氢化硅烷化;锌催化剂;吊坠供体;

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