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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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Item Permalink: http://hdl.handle.net/21.11116/0000-0005-A9FC-1 Version Permalink: http://hdl.handle.net/21.11116/0000-0005-A9FD-0
Genre: Journal Article

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 Creators:
Cheng, Jun, Author
Liu, Jian, Author
Leng, Xuebing, Author
Lohmiller, Thomas, Author
Schnegg, Alexander1, Author              
Bill, Eckhard1, Author              
Ye, Shengfa, Author
Deng, Liang, Author
Affiliations:
1Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              

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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; Ar-Trip = 2,6-bis(2',4',6'-triisopropylphenyl)phenyl) prepared from the reaction of an iron(0) complex with the bulky azide (ArN3)-N-Trip. 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) angstrom 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 pi acid, readily afford nitrene transfer products, (ArCH)-C-CF3=CHNHArTrip and (ArNCO)-N-Trip, respectively, yet no similar reaction occurs when 3 is treated with electron rich alkenes and PMe3. Moreover, 3 is inert toward the weak C(sp(3))-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(sp(3))-H bond functionalization was observed by adding (p-Tol)(2)CN2 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
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
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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