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  A Two-Coordinate Iron(II) Imido Complex with NHC Ligation: Synthesis, Characterization, and Its Diversified Reactivity of Nitrene Transfer and C–H Bond Activation

Cheng, J., Liu, J., Leng, X., Lohmiller, T., Schnegg, A., Bill, E., et al. (2019). A Two-Coordinate Iron(II) Imido Complex with NHC Ligation: Synthesis, Characterization, and Its Diversified Reactivity of Nitrene Transfer and C–H Bond Activation. Inorganic Chemistry, 58(11), 7634-7644. doi:10.1021/acs.inorgchem.9b01147.

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 Creators:
Cheng, Jun1, Author
Liu, Jian1, Author
Leng, Xuebing1, Author
Lohmiller, Thomas2, Author
Schnegg, Alexander3, Author           
Bill, Eckhard3, Author           
Ye, Shengfa4, Author           
Deng, Liang1, Author
Affiliations:
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People’s Republic of China, ou_persistent22              
2Berlin Joint EPR Lab, Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin, Germany, ou_persistent22              
3Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
4Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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 Abstract: Iron terminal imido species are typically implicated as reaction intermediates in iron-catalyzed transformations. While a large body of work has been devoted to mid- and high-valent iron imidos, to date the chemistry of iron(II) imidos has remained largely unexplored due to the difficulty in accessing them. Herein, we present a study on the two-coordinate iron(II) imido complex [(IPr)Fe(NArTrip)] (3; IPr = 1,3-bis(2′,6′-diisopropylphenyl)imidazol-2-ylidene; ArTrip = 2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl) prepared from the reaction of an iron(0) complex with the bulky azide ArTripN3. Spectroscopic investigations in combination with DFT calculations established a high-spin S = 2 ground spin state for 3, consistent with its long Fe–N multiple bond of 1.715(2) Å revealed by X-ray diffraction analysis. Complex 3 exhibits unusual activity of nitrene transfer and C–H bond activation in comparison to the reported iron imido complexes. Specifically, the reactions of 3 with CH2═CHArCF3, an electron-deficient alkene, and CO, a strong π acid, readily afford nitrene transfer products, ArCF3CH═CHNHArTrip and ArTripNCO, respectively, yet no similar reaction occurs when 3 is treated with electron-rich alkenes and PMe3. Moreover, 3 is inert toward the weak C(sp3)–H bonds in 1,4-cyclohexadiene, THF, and toluene, whereas it can cleave the stronger C(sp)–H bond in p-trifluoromethylphenylacetylene to form an iron(II) amido alkynyl complex. Interestingly, intramolecular C(sp3)–H bond functionalization was observed by adding (p-Tol)2CN2 to 3. The unique reactivity of 3 is attributed to its low-coordinate nature and the high negative charge population on the imido N atom, which render its iron–imido unit nucleophilic in nature.

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Language(s): eng - English
 Dates: 2019-04-192019-05-142019-06-03
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.9b01147
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 58 (11) Sequence Number: - Start / End Page: 7634 - 7644 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669