Tracking an FeV(O) Intermediate for Water Oxidation in Water

High‐valent iron‐oxo species are appealing for conducting O−O bond formation for water oxidation reactions. However, their high reactivity poses a great challenge to the dissection of their chemical transformations. Herein, we introduce an electron‐rich and oxidation‐resistant ligand, 2‐[(2,2′‐bipyr...

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Bibliographic Details
Published in:Angewandte Chemie 2023-09, Vol.135 (36), p.n/a
Main Authors: Wei, Xiang‐Zhu, Ding, Tian‐Yu, Wang, Yang, Yang, Bing, Yang, Qing‐Qing, Ye, Shengfa, Tung, Chen‐Ho, Wu, Li‐Zhu
Format: Article
Language:English
Subjects:
Bonding
Chemical reactions
Chemistry
Electrochemistry
Homogenous Catalysis
Intermediates
Iron-Based Complex
Labeling
Oxidation
Oxidation resistance
Oxygen isotopes
O−O Bond Formation
Reactive Intermediate
Water Oxidation
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Summary:High‐valent iron‐oxo species are appealing for conducting O−O bond formation for water oxidation reactions. However, their high reactivity poses a great challenge to the dissection of their chemical transformations. Herein, we introduce an electron‐rich and oxidation‐resistant ligand, 2‐[(2,2′‐bipyridin)‐6‐yl]propan‐2‐ol to stabilize such fleeting intermediates. Advanced spectroscopies and electrochemical studies demonstrate a high‐valent FeV(O) species formation in water. Combining kinetic and oxygen isotope labelling experiments and organic reactions indicates that the FeV(O) species is responsible for O−O bond formation via water nucleophilic attack under the real catalytic water oxidation conditions. An electron‐rich and oxidation‐resistant ligand is effective at stabilizing high‐valent iron‐oxo intermediates involved in the water oxidation reaction. UV/Vis, XAS, EPR, electrochemical and kinetic measurements, allow a high‐valent FeV(O) species that participates in O−O bond formation with higher reactivity and shorter lifetime to be tracked in a real catalytic water oxidation reaction.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202308192