Redox Behavior and Kinetics of Hydroxo Ligand Exchange on Iron Tetraphenylporphyrin. Comparison with Chloro Exchange and Consequences for its Role in Self-Modulation of Molecular Catalysis of Electrochemical Reactions - Archive ouverte HAL
Article Dans Une Revue Inorganic Chemistry Année : 2024

Redox Behavior and Kinetics of Hydroxo Ligand Exchange on Iron Tetraphenylporphyrin. Comparison with Chloro Exchange and Consequences for its Role in Self-Modulation of Molecular Catalysis of Electrochemical Reactions

Résumé

Thermodynamics and kinetics of hydroxide ion binding to iron tetraphenylporphyrin (TPPFe) at different redox states is investigated by electrochemistry and UV-vis spectroscopy. The reduction of TPPFe drastically decreases the binding affinity of hydroxide ions. An activation-driving force correlation is revealed showing that the strongest the binding affinity, the largest the association rate constant and vice-versa. Comparison with chloride ions shows that hydroxide ions are stronger ligands for iron tetraphenylporphyrin. However, kinetic data indicate that coordination and de-coordination of chloride ions is intrinsically faster than coordination and de-coordination of hydroxide ions. Finally, the consequence of hydroxide ion binding dynamics when TPPFe is used as a molecular catalyst for electrochemical reactions liberating hydroxides is discussed in the framework of self-modulation of catalytic processes.

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hal-04682321 , version 1 (30-08-2024)

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Camille Chartier, Sylvie Chardon-Noblat, Cyrille Costentin. Redox Behavior and Kinetics of Hydroxo Ligand Exchange on Iron Tetraphenylporphyrin. Comparison with Chloro Exchange and Consequences for its Role in Self-Modulation of Molecular Catalysis of Electrochemical Reactions. Inorganic Chemistry, 2024, 63 (17), pp.7541-7548. ⟨10.1021/acs.inorgchem.4c00825⟩. ⟨hal-04682321⟩
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