Transformation of a Cp*-iridium carbene catalyst in water oxidation using Oxone as primary oxidant

Fundamental understanding of the real catalytic species in water oxidation is a major knowledge gap that must be overcome in order to develop artificial water splitting systems and produce chemical fuels from solar energy. In an effort to analyze the transformation and catalytic resting state of [Cp*Ir(pmNHC)Cl]Cl [pmNHC = 1-(2-pyrimidyl)-3- n -butylimidazol-2-ylidene, Cp* = pentamethylcyclopentadienyl] in water oxidation using potassium peroxymonosulfate (Oxone) as primary oxidant, we found the precatalyst evolved into blue solution when a small amount of Oxone was added while further oxidation yield purple solution. These species have been proven to be homogeneous and they remain active in water oxidation. 1 H NMR profiles and MALDI-MS data suggested a rapid oxidation of the Cp* ligand to acetone, formic and acetic acid. 1 H NMR, TEM-EDX as well as MALDI-MS data indicated a continuous degradation of pyrimidyl, butyl and NHC groups. MALDI-MS, XANES and 17 O NMR spectroscopy data of the blue species are most consistent with an iridium(III) compound with two waters, one dioxygen and pmNHC group. The catalytic resting purple species probably consists of an iridium(III) complex with three waters, one chloride and one bicarbonate ligand. Besides, the presence of a small amount of iridium aqua ion oligomers was observed in the purple species. The formation of polymers and nanoparticles is likely to be inhibited by the acid environment.