Electrochemical and Kinetic Insights into Molecular Water Oxidation Catalysts Derived from Cp*Ir(pyridine-alkoxide) Complexes.

We report the solution-phase electrochemistry of seven half-sandwich iridium(III) complexes with varying pyridine-alkoxide ligands to quantify electronic ligand effects that translate to their activity in catalytic water oxidation. Our results unify some previously reported electrochemical data of CpIr complexes by showing how the solution speciation determines the electrochemical response: cationic complexes show over 1 V higher redox potentials that their neutral forms in a distinct demonstration of charge accumulation effects relevant to water oxidation. Building on previous work that analysed the activation behaviour of our pyalk-ligated CpIr complexes -, we assess their catalytic oxygen evolution activity with sodium periodate (NaIO) and ceric ammonium nitrate (CAN) in water and aqueous BuOH solution. Mechanistic studies including H/D kinetic isotope effects and reaction progress kinetic analysis (RPKA) of oxygen evolution point to a dimer-monomer equilibrium of the Ir resting state preceding a proton-coupled electron transfer (PCET) in the turnover-limiting step (TLS). Finally, true electrochemically driven water oxidation is demonstrated for all catalysts, revealing surprising trends in activity that do not correlate with those obtained using chemical oxidants.