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Secondary Sphere Effects on Porous Polymeric Organocatalysts for CO2 Transformations: Subtle Modifications Resulting in Superior Performance.
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-06-29 , DOI: 10.1021/acsami.0c08817 Yanpei Song 1 , Qi Sun 2 , Pui Ching Lan 1 , Shengqian Ma 1
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-06-29 , DOI: 10.1021/acsami.0c08817 Yanpei Song 1 , Qi Sun 2 , Pui Ching Lan 1 , Shengqian Ma 1
Affiliation
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Albeit harnessing secondary sphere interactions to exert control over the reaction outcomes has primarily been applied to enzymatic and organometallic catalysis, there are seldom any studies that introduce outer-sphere modifiers into organocatalysts. This is even less in the corresponding heterogeneous catalytic system. In this contribution, we experimentally and computationally investigate the role of secondary effects in the reactivity of bromide anions toward CO2 transformations. Six pyridinium cationic porous frameworks have been synthesized and fully characterized. Structure–activity relationships and kinetics show that the type and the location of the substituents on the cationic framework have a significant impact on the nucleophilic reactivity of their bromide counter anion. Specifically, the attachment of amine substituent to the ortho position relative to a pyridinium motif produces a remarkably efficient catalyst for CO2 transformation, by a factor of six times greater in comparison to the pristine pyridinium-based polymer. The hydrogen-bond-interaction-promoted reagent activation and enhanced delocalization ability of bromide counter anion are believed to be the key to driving the reaction toward CO2 utilization. These observations, therefore, champion the leverage of secondary interaction for optimizing the reactivity of organocatalysts.
中文翻译：
次生球体对多孔聚合物有机催化剂进行CO2转化的影响：导致卓越性能的细微修饰。
尽管利用二级球相互作用来控制反应结果已主要应用于酶催化和有机金属催化，但很少有研究将外球改性剂引入有机催化剂。在相应的非均相催化体系中甚至更少。在这项贡献中，我们通过实验和计算方法研究了次要作用在溴化物阴离子对CO 2反应性中的作用转变。已合成并充分表征了六个吡啶鎓阳离子多孔骨架。结构-活性之间的关系和动力学表明，取代基的类型和位置在阳离子骨架上对其溴化物抗衡阴离子的亲核反应性有重大影响。具体而言，胺取代基相对于吡啶鎓基序的邻位的连接产生了非常有效的CO 2转化催化剂，是原始吡啶鎓基聚合物的六倍。氢键相互作用促进的试剂活化和溴化物抗衡阴离子的增强的离域能力被认为是推动反应向CO 2转化的关键利用率。因此，这些观察结果支持了次级相互作用对优化有机催化剂反应性的影响。
更新日期：2020-07-22
中文翻译：
次生球体对多孔聚合物有机催化剂进行CO2转化的影响：导致卓越性能的细微修饰。
尽管利用二级球相互作用来控制反应结果已主要应用于酶催化和有机金属催化，但很少有研究将外球改性剂引入有机催化剂。在相应的非均相催化体系中甚至更少。在这项贡献中，我们通过实验和计算方法研究了次要作用在溴化物阴离子对CO 2反应性中的作用转变。已合成并充分表征了六个吡啶鎓阳离子多孔骨架。结构-活性之间的关系和动力学表明，取代基的类型和位置在阳离子骨架上对其溴化物抗衡阴离子的亲核反应性有重大影响。具体而言，胺取代基相对于吡啶鎓基序的邻位的连接产生了非常有效的CO 2转化催化剂，是原始吡啶鎓基聚合物的六倍。氢键相互作用促进的试剂活化和溴化物抗衡阴离子的增强的离域能力被认为是推动反应向CO 2转化的关键利用率。因此，这些观察结果支持了次级相互作用对优化有机催化剂反应性的影响。
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