Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst
Authors:
- Salvador B. MuñozSMSalvador B. Muñoz
- Diane A. DickieDiane A. Dickie
- Jeremy M. SmithJeremy M. Smith
- 15 July 2014
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 53 (37) , 9856-9859
Abstract
The catalytic reactivity of the high‐spin MnII pyridinophane complexes [(Py2NR2)Mn(H2O)2]2+ (R=H, Me, tBu) toward O2 formation is reported. With small macrocycle N‐substituents (R=H, Me), the complexes catalytically disproportionate H2O2 in aqueous solution; with a bulky substituent (R=tBu), this catalytic reaction is shut down, but the complex becomes active for aqueous electrocatalytic H2O oxidation. Control experiments are in support of a homogeneous molecular catalyst and preliminary mechanistic studies suggest that the catalyst is mononuclear. This ligand‐controlled switch in catalytic reactivity has implications for the design of new manganese‐based water oxidation catalysts.Keywords
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