Atropisomeric Effects of Second Coordination Spheres on Electrocatalytic CO2 Reduction,ChemCatChem

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Atropisomeric Effects of Second Coordination Spheres on Electrocatalytic CO2 Reduction
ChemCatChem ( IF 3.8 ) Pub Date : 2020-06-22 , DOI: 10.1002/cctc.202000909
Caroline K. Williams ₁ , Amir Lashgari ₁ , Jenny A. Tomb ₁ , Jingchao Chai ₁ , Jianbing Jimmy Jiang ₁

Affiliation

Control of the second coordination spheres of molecular catalytic systems has enhanced the catalytic efficiencies and facilitated the elucidation of catalytic mechanisms. Herein, we present the evaluation of stereoisomeric effects of a set of metal redox‐innocent zinc porphyrin complexes on CO₂ reduction, including complexes containing four (ZnP4T) and one (ZnP1T) triazole units, and two atropisomers with two triazole units positioned at the same (ZnP2T‐αα) and different (ZnP2T‐αβ) sides of the zinc porphyrin framework. Kinetic study and foot‐of‐the‐wave analysis indicated that complexes with more than one triazole unit on the same side of the porphyrin framework (ZnP4T and ZnP2T‐αα) display at least double maximum turnover frequency than the counterparts with a single triazole unit on the same side (ZnP1T and ZnP2T‐αβ). These results suggest the formation of a hydrogen‐bonding network in the second coordination sphere that facilitates proton transfer from the hydrophilic network to the catalyst‐CO₂ intermediate.

中文翻译：

第二配位球的阻转异构作用对电催化二氧化碳还原的影响

控制分子催化系统的第二配位域提高了催化效率并促进了催化机理的阐明。本文中，我们介绍了一组金属氧化还原-无毒锌卟啉配合物对CO ₂还原的立体异构效应的评估，包括包含四个（ZnP4T）和一个（ZnP1T）三唑单元的配合物，以及两个在两个三唑单元处的阻转异构体。锌卟啉骨架的同一侧（ZnP2T-αα）和不同侧（ZnP2T-αβ）。动力学研究和波峰分析表明，在卟啉骨架的同一侧（ZnP4T和ZnP2T‐αα）的最大周转频率至少是同一侧具有单个三唑单元的同类产品（ZnP1T和ZnP2T‐αβ）的两倍。这些结果表明在第二配位球中形成了氢键网络，该氢键网络促进了质子从亲水网络转移到催化剂CO ₂中间体的过程。

更新日期：2020-06-22

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