Diane Dickie - Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst.

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      Lee, Wei-Tsung, Munoz, Salvador B., III, Dickie, Diane A., Smith,   Jeremy M. Angewandte Chemie, International Edition  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 aq. soln.; with a bulky substituent   (R=tBu), this catalytic reaction is shut down, but the complex   becomes active for aq. electrocatalytic H2O oxidn. Control expts.   are in support of a homogeneous mol. 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 oxidn.   catalysts. [on SciFinder(R)]

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