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

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 initial TPPFe­(III) 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 decoordination of chloride ions is intrinsically faster than coordination and decoordination 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.