biostudies-literatureOloo WNOrsz??gos Tudom??nyos Kutat??si AlapprogramokNational Institute of General Medical SciencesNIGMS NIH HHS37-41https://www.ebi.ac.uk/biostudies/studies/S-EPMC8958355biostudies-literatureUnknown61(1)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 (μ-oxo)(μ-1,2-peroxo)diiron(III) intermediate (<b>2</b>) that is capable of olefin epoxidation and alkane hydroxylation including cyclohexane. Species <b>2</b> 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 H₂¹⁸O 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 O₂-activating nonheme diiron enzymes.Inorganic chemistryNonheme Diiron Oxygenase Mimic That Generates a Diferric-Peroxo Intermediate Capable of Catalytic Olefin Epoxidation and Alkane Hydroxylation Including Cyclohexane.PMC8958355TKP2020-IKA-07R01 GM-38767R35 GM131721GINOP-2.3.2-15-2016-00049R35 GM-131721K108489R01 GM038767Que LKaizer JSzavuly MOloo WNfalseNonheme Diiron Oxygenase Mimic That Generates a Diferric-Peroxo Intermediate Capable of Catalytic Olefin Epoxidation and Alkane Hydroxylation Including Cyclohexane.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 (μ-oxo)(μ-1,2-peroxo)diiron(III) intermediate (<b>2</b>) that is capable of olefin epoxidation and alkane hydroxylation including cyclohexane. Species <b>2</b> 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 H₂¹⁸O 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 O₂-activating nonheme diiron enzymes.2022-01-01T00:00:00Z2022 Jan2025-04-05T22:19:02.266Z2025-04-05T22:19:02.266ZS-EPMC89583553489468310.1021/acs.inorgchem.1c03468