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Angew Chem Int Ed Engl. 2014 Sep 8;53(37):9856-9. doi: 10.1002/anie.201402407. Epub 2014 Jul 15.

Ligand modification transforms a catalase mimic into a water oxidation catalyst.

Author information

  • 1Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, IN 47405 (USA).

Abstract

The catalytic reactivity of the high-spin Mn(II) 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.

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

KEYWORDS:

catalysis; macrocycles; manganese; molecular electrochemistry; water splitting

PMID:
25044487
[PubMed - in process]
PMCID:
PMC4167389
[Available on 2015/9/8]
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