John Wiley and Sons Ltd;Weinheim: WILEY-VCH Verlag
摘要:
摘要： 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. Ligand‐controlled switch: Simple modification of the substituent on a pyridinophane macrocycle ligand converts the corresponding MnII complex from a hydrogen peroxide disproportionation catalyst into a water oxidation catalyst. Preliminary results indicate that the catalyst is mononuclear. 其他題名： Angew. Chem. Int. Ed 出版者： Weinheim: WILEY-VCH Verlag 出版日期： 2014-09-08 出處： Angewandte Chemie International Edition, 2014-09, Vol.53 (37), p.9856-9859 資源來源： Wiley Online Journals ** 版權： 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim 版權： 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 版權： 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 版權： Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 識別號： ISSN: 1433-7851 識別號： ISSN: 1521-3773 識別號： EISSN: 1521-3773 識別號： DOI: 10.1002/anie.201402407 識別號： PMID: 25044487 識別號： CODEN: ACIEAY
