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Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst
Author(s) -
Lee WeiTsung,
Muñoz Salvador B.,
Dickie Diane A.,
Smith Jeremy M.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201402407
Subject(s) - catalysis , reactivity (psychology) , chemistry , ligand (biochemistry) , aqueous solution , manganese , catalytic oxidation , homogeneous catalysis , substituent , redox , medicinal chemistry , inorganic chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
Abstract The catalytic reactivity of the high‐spin Mn II pyridinophane complexes [(Py 2 NR 2 )Mn(H 2 O) 2 ] 2+ (R=H, Me, t Bu) toward O 2 formation is reported. With small macrocycle N‐substituents (R=H, Me), the complexes catalytically disproportionate H 2 O 2 in aqueous solution; with a bulky substituent (R= t Bu), this catalytic reaction is shut down, but the complex becomes active for aqueous electrocatalytic H 2 O 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.