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首页> 外文期刊>Organometallics >Catalytic Preparation of Cyclic Carbonates from CO2 and Epoxides by Metal–Porphyrin and ?Corrole Complexes: Insight into Effects of Cocatalyst and meso-Substitution
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Catalytic Preparation of Cyclic Carbonates from CO2 and Epoxides by Metal–Porphyrin and ?Corrole Complexes: Insight into Effects of Cocatalyst and meso-Substitution

机译：通过金属 - 卟啉和αα和αα和α和αα和氧化环氧化酯的催化制备碳酸环碳酸酯和氧化氢硅酸盐：对助催化剂和 Meso -subst原样的洞察

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摘要

Extensive DFT calculations have been performed to elucidate the plausible mechanisms and effects of the cocatalyst and meso -substitution of the macro ring on the coupling reaction of CO_(2) with epoxide catalyzed by metal prophyrin and corrole complexes. Here the catalytic generation of cyclic carbonate from CO_(2) and epoxide by the Al–, Mg–, and Zn–porphyrin catalysts is predicted to follow a similar multistep mechanism, in which the ring-opening and -closure steps experience relatively high free energy barriers, while the CO_(2) insertion is facile. The computational results lend support to the remarkable catalytic role of a quaternary ammonium salt cocatalyst in the order PPNCl > PPNBr > PPNI. Introduction of the aryl and chlorinated aryl substituents on the porphyrin ligand reduces the electrophilicity of an aluminum center to some extent but remarkably enhances binding interactions among catalyst, cocatalyst, and reactant, which may facilitate the initial reaction. The ring-closure step is less influenced by the meso -substitution. The corrole-based complexes have similar catalytic behaviors, and they are also promising catalysts for the cycloaddition of CO_(2) to epoxides.
机译：已经进行了广泛的DFT计算，以阐明宏观环和中学 - 甲基磷酸盐的合理机制和效果在金属预防和腐蚀复合物催化的环氧化物的CO_（2）的偶联反应上。这里预测来自CO_（2）和Zn-卟啉催化剂的CO_（2）和环氧化锌的催化产生遵循类似的多中间机制，其中开环和缩放步骤经验相对较高能量屏障，而CO_（2）插入是便于的。计算结果对PPNCl> PPNBR> PPNI顺序的季铵盐助催化剂的显着催化作用提供了支持。在卟啉配体上引入芳基和氯化芳基取代基在一定程度上降低了铝中心的亲电性，但是显着增强了催化剂，助催化剂和反应物之间的结合相互作用，这可以促进初始反应。闭环步骤的影响较小，受到Meso -substitut的影响。基于符合符合符合的催化性能具有相似的催化性能，并且它们也是环形加入的催化剂，用于环氧化的CO_（2）。

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  • 来源
    《Organometallics》 |2018年第3期|共9页
  • 作者

    Ping Li; Zexing Cao;

  • 作者单位

    State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China;

    State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China;

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  • 正文语种 eng
  • 中图分类 元素有机化合物;
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