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  A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N–O Reagent as the “Amino” Source and “Oxidant”

Chatterjee, S., Harden, I., Bistoni, G., Castillo, R. G., Chabbra, S., van Gastel, M., et al. (2022). A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N–O Reagent as the “Amino” Source and “Oxidant”. Journal of the American Chemical Society, 144(6), 2637-2656. doi:10.1021/jacs.1c11083.

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Chatterjee, Sayanti1, 2, Author              
Harden, Ingolf3, Author              
Bistoni, Giovanni3, Author              
Castillo, Rebeca G.1, Author
Chabbra, Sonia1, Author              
van Gastel, Maurice4, Author              
Schnegg, Alexander1, Author              
Bill, Eckhard1, Author              
Birrell, James A.1, Author              
Morandi, Bill2, 5, Author              
Neese, Frank6, Author              
DeBeer, Serena1, Author              
Affiliations:
1Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
2Research Group Morandi, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2040309              
3Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541703              
4Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
5ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland, ou_persistent22              
6Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: Herein, we study the mechanism of iron-catalyzed direct synthesis of unprotected aminoethers from olefins by a hydroxyl amine derived reagent using a wide range of analytical and spectroscopic techniques (Mössbauer, Electron Paramagnetic Resonance, Ultra-Violet Visible Spectroscopy, X-ray Absorption, Nuclear Resonance Vibrational Spectroscopy, and resonance Raman) along with high-level quantum chemical calculations. The hydroxyl amine derived triflic acid salt acts as the “oxidant” as well as “amino” group donor. It activates the high-spin Fe(II) (St = 2) catalyst [Fe(acac)2(H2O)2] (1) to generate a high-spin (St = 5/2) intermediate (Int I), which decays to a second intermediate (Int II) with St = 2. The analysis of spectroscopic and computational data leads to the formulation of Int I as [Fe(III)(acac)2-N-acyloxy] (an alkyl-peroxo-Fe(III) analogue). Furthermore, Int II is formed by N–O bond homolysis. However, it does not generate a high-valent Fe(IV)(NH) species (a Fe(IV)(O) analogue), but instead a high-spin Fe(III) center which is strongly antiferromagnetically coupled (J = −524 cm–1) to an iminyl radical, [Fe(III)(acac)2-NH·], giving St = 2. Though Fe(NH) complexes as isoelectronic surrogates to Fe(O) functionalities are known, detection of a high-spin Fe(III)-N-acyloxy intermediate (Int I), which undergoes N–O bond cleavage to generate the active iron–nitrogen intermediate (Int II), is unprecedented. Relative to Fe(IV)(O) centers, Int II features a weak elongated Fe–N bond which, together with the unpaired electron density along the Fe–N bond vector, helps to rationalize its propensity for N-transfer reactions onto styrenyl olefins, resulting in the overall formation of aminoethers. This study thus demonstrates the potential of utilizing the iron-coordinated nitrogen-centered radicals as powerful reactive intermediates in catalysis.

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Language(s): eng - English
 Dates: 2021-10-242022-02-042022-02-16
 Publication Status: Published in print
 Pages: 20
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c11083
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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: 144 (6) Sequence Number: - Start / End Page: 2637 - 2656 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870