Heterogenized Water Oxidation Catalysts Prepared by Immobilizing Kläui-Type Organometallic Precursors

An efficient heterogenized water oxidation cata- lyst (2_TiO2) has been synthesized by immobilizing the Kläui-type organometallic precursor [Cp*Ir{P(O)(OH)2}3]Na (2, Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl ligand) onto rutile TiO2. Iridium is homogeneously distributed at the molecular and atomic/small cluster level in 2_TiO2 and 2’_TiO2 (solid catalyst recovered after the first catalytic run), respectively, as indicated by STEM-HAADF (scanning transmission electron microscopy - high angle annular dark field) studies. 2’_TiO2 exhibits TOF values up to 23.7 min 1 in the oxidation of water to O2 driven by NaIO4 at nearly neutral pH, and a TON only limited by the amount of NaIO4 used, as indicated by multiple run ex- periments. Furthermore, while roughly 40% leaching is observed during the first catalytic run, 2’_TiO2 does not undergo any further leaching even when in contact with strongly basic solutions and completely maintains its ac- tivity for thousands of cycles. NMR studies, in combination with ICP-OES (inductively coupled plasma optical emission spectrometry), indicate that the activation of 2_TiO2 occurs through the initial oxidative dissociation of PO43 , ultimately leading to active centers in which a 1:1 P/Ir ratio is present (derived from the removal of two PO43 units) likely missing the Cp* ligand.