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  Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O-2 at an Iron(II)-Cyclam Center

Kass, D., Corona, T., Warm, K., Braun-Cula, B., Kuhlmann, U., Bill, E., et al. (2020). Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O-2 at an Iron(II)-Cyclam Center. Journal of the American Chemical Society, 142(13), 5924-5928. doi:10.1021/jacs.9b13756.

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 Creators:
Kass, Dustin, Author
Corona, Teresa, Author
Warm, Katrin, Author
Braun-Cula, Beatrice, Author
Kuhlmann, Uwe, Author
Bill, Eckhard1, Author           
Mebs, Stefan, Author
Swart, Marcel, Author
Dau, Holger, Author
Haumann, Michael, Author
Hildebrandt, Peter2, 3, Author           
Ray, Kallol4, Author           
Affiliations:
1Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
2Department of Spectroscopy and Photochemical Kinetics, MPI for biophysical chemistry, Max Planck Society, ou_578624              
3Abteilung Spektroskopie, MPI for biophysical chemistry, Max Planck Society, ou_578545              
4External Organizations, ou_persistent22              

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 Abstract: In soluble methane monooxygenase enzymes (sMMO), dioxygen (O-2) is activated at a diiron(II) center to form an oxodiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O-2 activation at mono- or dinuclear iron centers is rare in the synthetic chemistry. Herein, we report a mononuclear non-heme iron(II)cyclam complex, 1-trans, that activates O-2 to form the corresponding iron(IV)-oxo complex, 2-trans, via a mechanism reminiscent of the O-2 activation process in sMMO. The conversion of 1-trans to 2-trans proceeds via the intermediate formation of an iron(III)-superoxide species 3, which could be trapped and spectroscopically characterized at -50 degrees C. Surprisingly, 3 is a stronger oxygen atom transfer (OAT) agent than 2-trans; 3 performs OAT to 1-trans or PPh 3 to yield 2-trans quantitatively. Furthermore, 2-trans oxidizes the aromatic C-H bonds of 2,6-di-tert-butylphenol, which, together with the strong OAT ability of 3, represents new domains of oxoiron(IV) and superoxoiron(III) reactivities.

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Language(s): eng - English
 Dates: 2020
 Publication Status: Issued
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: ISI: 000526393700003
DOI: 10.1021/jacs.9b13756
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (13) Sequence Number: - Start / End Page: 5924 - 5928 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870