Role‐Specialized Division of Labor in CO2 Reduction with Doubly‐Functionalized Iron Porphyrin Atropisomers

In enzymes, the active site residues function differently to promote chemical reactions. Such a role‐specialized division of labor has been rarely realized by synthetic catalysts. We report herein on catalytic CO2 reduction with Fe porphyrins decorated with two cationic N,N,N‐trimethylbenzylamine gr...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-08, Vol.61 (35), p.e202209602-n/a
Main Authors: Guo, Kai, Li, Xialiang, Lei, Haitao, Guo, Hongbo, Jin, Xiaotong, Zhang, Xue‐Peng, Zhang, Wei, Apfel, Ulf‐Peter, Cao, Rui
Format: Article
Language:English
Subjects:
Acetonitrile
Atropisomers
Carbon dioxide
Catalysts
Cations
Chemical reactions
CO2 Reduction
Division of Labor
Electrostatic properties
Iron
Iron Porphyrins
Isomers
Labor
Molecular Electrocatalysis
Phenols
Porphyrins
Reduction
Substrates
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Summary:In enzymes, the active site residues function differently to promote chemical reactions. Such a role‐specialized division of labor has been rarely realized by synthetic catalysts. We report herein on catalytic CO2 reduction with Fe porphyrins decorated with two cationic N,N,N‐trimethylbenzylamine groups in cis‐ or trans‐arrangement. The cis‐isomer outperforms the trans‐isomer and reaches a TOFmax of 4.4×105 s−1 in acetonitrile using phenol proton source. Theoretical studies revealed that the two cationic units in the cis‐isomer are more effective than a single cationic unit to improve the CO2 binding, and more importantly, they function differently but cooperatively to promote the C−O bond cleavage: one interacts with the CO2‐adduct, while the other one interacts with the phenol molecule through electrostatic interactions. This work therefore presents a significant example of synthetic catalysts, which boost chemical reactions using a role‐specialized strategy for substrate activation. A Fe porphyrin decorated with two cationic units in a cis‐arrangement was synthesized and showed exceptionally high activity for the electrocatalytic CO2‐to‐CO conversion. Theoretical studies revealed that the two cationic units function differently but cooperatively to promote the C−O bond cleavage. This work presents a significant example of synthetic catalysts, which use a role‐specialized division of labor strategy in small‐molecule activation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202209602