期刊
INORGANIC CHEMISTRY
卷 61, 期 1, 页码 37-41出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03468
关键词
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资金
- Hungarian Research Fund [K108489, TKP2020-IKA-07, GINOP-2.3.2-15-2016-00049]
- U.S. National Institutes of Health [R01 GM-38767, R35 GM-131721]
This study elucidates the substrate oxidations catalyzed by [Fe-II(IndH)(CH3CN)(3)](ClO4)(2) with H2O2, resulting in the formation of a spectroscopically characterized (mu-oxo)(mu-1,2-peroxo)diiron(III) intermediate capable of various oxidative reactions including epoxidation and hydroxylation.
Herein are described substrate oxidations with H2O2 catalyzed by [Fe-II(IndH)(CH3CN)(3)](ClO4)(2) [IndH = 1,3-bis(2'-pyridylimino)isoindoline], involving a spectroscopically characterized (mu-oxo)(mu-1,2-peroxo)diiron(III) intermediate (2) that is capable of olefin epoxidation and alkane hydroxylation including cyclohexane. Species 2 also converts ketones to lactones with a decay rate dependent on [ketone], suggesting direct nucleophilic attack of the substrate carbonyl group by the peroxo species. In contrast, peroxo decay is unaffected by the addition of olefins or alkanes, but the label from (H2O)-O-18 is incorporated into the the epoxide and alcohol products, implicating a high-valent iron-oxo oxidant that derives from O-O bond cleavage of the peroxo intermediate. These results demonstrate an ambiphilic diferric-peroxo intermediate that mimics the range of oxidative reactivities associated with O-2-activating nonheme diiron enzymes.
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