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Structure and reactivity of a mononuclear non-haem iron(III)-peroxo complex

Title
Structure and reactivity of a mononuclear non-haem iron(III)-peroxo complex
Authors
Cho J.Jeon S.Wilson S.A.Liu L.V.Kang E.A.Braymer J.J.Lim M.H.Hedman B.Hodgson K.O.Valentine J.S.Solomon E.I.Nam W.
Ewha Authors
남원우조재흥Joan S. Valentine
SCOPUS Author ID
남원우scopus; Joan S. Valentinescopus
Issue Date
2011
Journal Title
Nature
ISSN
0028-0836JCR Link
Citation
vol. 478, no. 7370, pp. 502 - 505
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Oxygen-containing mononuclear iron species-iron(iii)-peroxo, iron(iii)-hydroperoxo and iron(iv)-oxo-are key intermediates in the catalytic activation of dioxygen by iron-containing metalloenzymes. It has been difficult to generate synthetic analogues of these three active iron-oxygen species in identical host complexes, which is necessary to elucidate changes to the structure of the iron centre during catalysis and the factors that control their chemical reactivities with substrates. Here we report the high-resolution crystal structure of a mononuclear non-haem side-on iron(iii)-peroxo complex, [Fe(iii)(TMC)(OO)] +. We also report a series of chemical reactions in which this iron(iii)-peroxo complex is cleanly converted to the iron(iii)-hydroperoxo complex, [Fe(iii)(TMC)(OOH)] 2+, via a short-lived intermediate on protonation. This iron(iii)-hydroperoxo complex then cleanly converts to the ferryl complex, [Fe(iv)(TMC)(O)] 2+, via homolytic O-O bond cleavage of the iron(iii)-hydroperoxo species. All three of these iron species-the three most biologically relevant iron-oxygen intermediates-have been spectroscopically characterized; we note that they have been obtained using a simple macrocyclic ligand. We have performed relative reactivity studies on these three iron species which reveal that the iron(iii)-hydroperoxo complex is the most reactive of the three in the deformylation of aldehydes and that it has a similar reactivity to the iron(iv)-oxo complex in C-H bond activation of alkylaromatics. These reactivity results demonstrate that iron(iii)-hydroperoxo species are viable oxidants in both nucleophilic and electrophilic reactions by iron-containing enzymes. © 2011 Macmillan Publishers Limited. All rights reserved.
DOI
10.1038/nature10535
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자연과학대학 > 화학·나노과학전공 > Journal papers
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