Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst

• DOI: 10.1002/ange.201402407
• Publication Date: 2014-07-15T20:13:22Z
• Authors: Wei‐Tsung Lee; Salvador B. Muñoz; Diane A. Dickie; Jeremy M. Smith
• Keywords: Reactivity; Homogeneous Catalysis; Catalytic Oxidation

Abstract The catalytic reactivity of the high‐spin Mn II pyridinophane complexes [(Py 2 NR )Mn(H O) ] 2+ (R=H, Me, t Bu) toward O formation is reported. With small macrocycle N‐substituents Me), catalytically disproportionate H in aqueous solution; with a bulky substituent (R= Bu), this reaction shut down, but complex becomes active for electrocatalytic oxidation. Control experiments are support homogeneous molecular catalyst and preliminary mechanistic studies suggest that mononuclear. This ligand‐controlled switch has implications design new manganese‐based water oxidation catalysts.