Kinetic Study and Nonlinear Phenomenon during the Copolymerization of CO2 with meso‐Epoxides Catalyzed by Various Bimetallic CoIII Complexes,Macromolecular Chemistry and Physics

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Kinetic Study and Nonlinear Phenomenon during the Copolymerization of CO2 with meso‐Epoxides Catalyzed by Various Bimetallic CoIII Complexes
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-10-01 , DOI: 10.1002/macp.202000247
Ye Liu ₁ , Yan Yu ₁ , Yuan‐Ye Bao ₁ , Xiao‐Bing Lu ₁

Affiliation

The privileged salen ligands coordinated with a metal center have demonstrated their successful applications in many challenging reactions. Moreover, their relatively straightforward preparations and an ease of structural modifications are also very attractive. The Co^III–salen complex has demonstrated to be one of the most efficient catalysts for the copolymerization of CO₂ with epoxides. Especially, the elaborate combination of two or more Co^III–salen units into one single molecule may enforce an intramolecular, cooperative reaction pathway, resulting in enhanced reaction rates or/and higher selectivities. Otherwise, the reactivity and/or selectivity will be reduced, or some side reactions may occur. Herein, various bimetallic Co^III complexes based on different linking groups are reported to bridge two salen planes, including flexible and rigid structures, together with their reactivities and selectivities toward copolymerization of CO₂ with meso‐epoxides. The asymmetric depletion in copolymerization CO₂ with cyclohexene oxide mediated by monometallic Co^III complex 2 is first observed, demonstrating the bimetallic mechanism; especially, the comparative kinetic measurements are performed as a function of reaction temperature to assess the activation barrier for production of copolymers for bi‐ and monometallic Co^III complexes. This study is expected to be instructive and meaningful to design more efficient bimetallic catalyst and to improve the copolymerization selectivity.

中文翻译：

多种双金属CoIII配合物催化CO2与内消旋环氧化合物共聚反应的动力学研究和非线性现象

与金属中心配衬的特权Salen配体已证明其在许多挑战性反应中的成功应用。此外，它们相对简单的制备方法和易于结构修饰的方法也很有吸引力。事实证明，Co ^III –salen配合物是CO ₂与环氧化物共聚的最有效催化剂之一。特别是，将两个或多个Co ^III -salen单元精心组合成一个分子可能会强制执行分子内协作反应途径，从而提高反应速率或/和更高的选择性。否则，反应性和/或选择性将降低，或者可能发生一些副反应。在此，各种双金属Co ^III基于不同的连接基团的复合物被报告给桥接两个沙仑飞机，包括柔性和刚性的结构，与它们的反应性和选择性朝向CO的共聚一起₂与内消旋环氧化物。首先观察到单金属Co ^III配合物2介导的CO ₂与环己烯的共聚合反应中的不对称消耗，表明了双金属机理。特别是，比较动力学测量是根据反应温度进行的，以评估生产双金属和单金属Co ^III的共聚物的活化障碍复合体。预期该研究对于设计更有效的双金属催化剂和提高共聚选择性具有指导意义。

更新日期：2020-11-04

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