Identifying Metal-Oxo/Peroxo Intermediates in Catalytic Water Oxidation by In Situ Electrochemical Mass Spectrometry.
J Am Chem Soc
; 144(39): 17748-17752, 2022 10 05.
Article
em En
| MEDLINE
| ID: mdl-36149317
ABSTRACT
Molecular catalysis of water oxidation has been intensively investigated, but its mechanism is still not yet fully understood. This study aims at capturing and identifying key short-lived intermediates directly during the water oxidation catalyzed by a cobalt-tetraamido macrocyclic ligand complex using a newly developed an in situ electrochemical mass spectrometry (EC-MS) method. Two key ligand-centered-oxidation intermediates, [(L2-)CoIIIOH] and [(L2-)CoIIIOOH], were directly observed for the first time, and further confirmed by 18O-labeling and collision-induced dissociation studies. These experimental results further confirmed the rationality of the water nucleophilic attack mechanism for the single-site water oxidation catalysis. This work also demonstrated that such an in situ EC-MS method is a promising analytical tool for redox catalytic processes, not only limited to water oxidation.
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2022
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