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  A Series of Iron Nitrosyl Complexes {Fe–NO}6–9 and a Fleeting {Fe–NO}10 Intermediate en Route to a Metalacyclic Iron Nitrosoalkane

Keilwerth, M., Hohenberger, J., Heinemann, F. W., Sutter, J., Scheurer, A., Fang, H., et al. (2019). A Series of Iron Nitrosyl Complexes {Fe–NO}6–9 and a Fleeting {Fe–NO}10 Intermediate en Route to a Metalacyclic Iron Nitrosoalkane. Journal of the American Chemical Society, 141(43), 17217-17235. doi:10.1021/jacs.9b08053.

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Keilwerth, Martin1, Author
Hohenberger, Johannes1, Author
Heinemann, Frank W.1, Author
Sutter, Jörg1, Author
Scheurer, Andreas1, Author
Fang, Huayi2, Author
Bill, Eckhard2, Author
Neese, Frank3, Author              
Ye, Shengfa4, Author              
Meyer, Karsten1, Author
Affiliations:
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University Erlangen-Nürnberg (FAU), Egerlandstrasse 1, D-91058 Erlangen, Germany, ou_persistent22              
2Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, D-45470 Mülheim an der Ruhr,Germany, ou_persistent22              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
4Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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 Abstract: Iron–nitrosyls have fascinated chemists for a long time due to the noninnocent nature of the NO ligand that can exist in up to five different oxidation and spin states. Coordination to an open-shell iron center leads to complex electronic structures, which is the reason Enemark−Feltham introduced the {Fe–NO}n notation. In this work, we succeeded in characterizing a series of {Fe–NO}6–9 complexes, including a reactive {Fe–NO}10 intermediate. All complexes were synthesized with the tris-N-heterocyclic carbene ligand tris[2-(3-mesitylimidazol-2-ylidene)ethyl]amine (TIMENMes), which is known to support iron in high and low oxidation states. Reaction of NOBF4 with [(TIMENMes)Fe]2+ resulted in formation of the {Fe–NO}6 compound [(TIMENMes)Fe(NO)(CH3CN)](BF4)3 (1). Stepwise chemical reduction with Zn, Mg, and Na/Hg leads to the isostructural series of high-spin iron nitrosyl complexes {Fe–NO}7,8,9 (2–4). Reduction of {Fe–NO}9 with Cs electride finally yields the highly reduced {Fe–NO}10 intermediate, key to formation of [Cs(crypt-222)][(TIMENMes)Fe(NO)], (5) featuring a metalacyclic [Fe−(NO−NHC)3−] nitrosoalkane unit. All complexes were characterized by single-crystal XRD analyses, temperature and field-dependent SQUID magnetization methods, as well as 57Fe Mössbauer, IR, UV/vis, multinuclear NMR, and dual-mode EPR spectroscopy. Spectroscopy-based DFT analyses provide insight into the electronic structures of all compounds and allowed assignments of oxidation states to iron and NO ligands. An alternative synthesis to the {Fe–NO}8 complex was found via oxygenation of the nitride complex [(TIMENMes)Fe(N)](BF4). Surprisingly, the resulting {Fe–NO}8 species is electronically and structural similar to the [(TIMENMes)Fe(N)]+ precursor. Based on the structural and electronic similarities between this nitrosyl/nitride complex couple, we adopted the strategy, developed by Wieghardt et al., of extending the Enemark−Feltham nomenclature to nitrido complexes, rendering [(TIMENMes)Fe(N)]+ as a {Fe–N}8 species.

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Language(s): eng - English
 Dates: 2019-07-272019-09-302019-10-30
 Publication Status: Published in print
 Pages: 21
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.9b08053
 Degree: -

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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 141 (43) Sequence Number: - Start / End Page: 17217 - 17235 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870