Mechanistic aspects of water oxidation catalyzed by organometallic iridium complexes

The reactions of three iridium water‐oxidation catalysts {[Cp*IrL¹L²L³]Xn; 1: L¹, L² = 2,2‐bipyridine (bpy), L³ = Cl, n = 1, X = Cl; 2: L¹, L² = 2‐benzoylpyridine (bzpy), L³ = NO₃; 3: L¹ = L² = L³ = H₂O, n = 2, X = NO₃; Cp* = pentamethylcyclopentadienyl} with cerium ammonium nitrate (CAN) and NaIO₄ (sacrificial oxidants, SOs) have been studied by Clark electrode measurements (both in solution and in the gas phase), on‐line mass spectrometry, manometry and UV/Vis spectroscopy. Furthermore, cyclic voltammetry has been applied to evaluate the relative tendency of 1 and 2 to be oxidized. The turnover frequency (TOF) increases as the ratio (R) between the concentration of the SO and that of the catalyst increases. O₂ production with CAN is observed in experiments with R = 20 for 1 and 3, whereas O₂ becomes detectable with 2 only when R = 40. Catalyst 2 has the highest tendency to be oxidized to IrIV and forms a blue intermediate I characterized by a UV/Vis band at 574 nm. The formation of I occurs with the same velocity as that of the production of O₂, which indicates that I is a species directly involved in the catalytic cycle. The disappearance of I, when O₂ evolution is finished, is a second‐order process more than one order of magnitude slower than O₂ production and is strongly accelerated by the presence of benzyl alcohol. This suggests that I is a molecular species that slowly undergoes disproportion when catalysis is over. Experiments in which multiple aliquots of SO (CAN) were added (R = 20 and 40) indicate that catalysts 1–3 can reinitiate the catalytic cycle once they have been kept in a dormant state for 0–9 min; the TOFs of the second and third additions are approximately equal and higher than that of the first addition. By combining manometry and on‐line mass spectrometry measurements, it was found that O₂ evolution is parallel to the production of a small amount of CO₂ owing to catalyst degradation. The TOFs of the experiments performed with NaIO₄ as the SO are about 2–3 times lower than those with CAN, but the same reactivity order is found 3 > 2 > 1. The activation parameters were evaluated with NaIO₄ for all catalysts and with CAN for 2 at 10–45 °C. ΔG^# is practically the same in all situations (25–26 kcal mol^–1), whereas ΔH^# is appreciably lower for 2 (13.1 kcal mol–1 with CAN and 13.3 kcal mol^–1 with NaIO₄) than for 1 (16 kcal mol^–1) and 3 (16.9 kcal mol^–1). The lowest enthalpic cost with 2 is balanced by the highest entropic cost (–41 cal mol^–1 K^–1) that approaches that typical for an associative bimolecular process.