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 Cp*Ir 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 Cp*Ir complexes 1-7, we assess their catalytic oxygen evolution activity with sodium periodate (NaIO4) and ceric ammonium nitrate (CAN) in water and aqueous tBuOH 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 IrIV 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.