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Demonstration of the Heterolytic OO Bond Cleavage of Putative Nonheme Iron(II)OOH(R) Complexes for Fenton and Enzymatic Reactions
Author(s) -
Bang Suhee,
Park Sora,
Lee YongMin,
Hong Seungwoo,
Cho KyungBin,
Nam Wonwoo
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201404556
Subject(s) - heterolysis , chemistry , alkyl , bond cleavage , medicinal chemistry , cleavage (geology) , photochemistry , catalysis , stereochemistry , organic chemistry , materials science , fracture (geology) , composite material
One‐electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe III OOH) and iron(III) alkylperoxo (Fe III OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one‐electron reduced iron(II) (hydro/alkyl)peroxo species is the rate‐determining step, followed by the heterolytic OO bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic OO bond‐cleavage mechanism. The present results provide the first example showing the one‐electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic OO bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions.