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  Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

Sabenya, G., Lázaro, L., Gamba, I., Martin-Diaconescu, V., Andris, E., Weyhermüller, T., et al. (2017). Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform. Journal of the American Chemical Society, 139(27), 9168-9177. doi:10.1021/jacs.7b00429.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0007-7931-A Version Permalink: http://hdl.handle.net/21.11116/0000-0007-7932-9
Genre: Journal Article

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 Creators:
Sabenya, Gerard1, Author
Lázaro, Laura1, Author
Gamba, Ilaria1, Author
Martin-Diaconescu, Vlad1, Author
Andris, Erik2, Author
Weyhermüller, Thomas3, Author              
Neese, Frank3, Author              
Roithova, Jana2, Author
Bill, Eckhard3, Author              
Lloret-Fillol, Julio4, 5, Author
Costas, Miquel1, Author
Affiliations:
1Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia, Spain, ou_persistent22              
2Department of Organic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 12843 Prague 2, Czech Republic, ou_persistent22              
3Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
4Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avinguda Paisos Catalans 16, 43007 Tarragona, Catalonia, Spain, ou_persistent22              
5Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluïs Companys 23, 08010 Barcelona, Spain, ou_persistent22              

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 Abstract: Iron complex [FeIII(N3)(MePy2tacn)](PF6)2 (1), containing a neutral triazacyclononane-based pentadentate ligand, and a terminally bound azide ligand has been prepared and spectroscopically and structurally characterized. Structural details, magnetic susceptibility data, and Mössbauer spectra demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe–N (1.859 Å) and long FeN–N2 (1.246 Å) distances, while the FT-IR spectra show an unusually low N–N stretching frequency (2019 cm–1), suggesting that the FeN–N2 bond is particularly weak. Photolysis of 1 at 470 or 530 nm caused N2 elimination and generation of a nitrido species that on the basis of Mössbauer, magnetic susceptibility, EPR, and X-ray absorption in conjunction with density functional theory computational analyses is formulated as [FeV(N)(MePy2tacn)]2+ (2). Results indicate that 2 is a low-spin (S = 1/2) iron(V) species, which exhibits a short Fe–N distance (1.64 Å), as deduced from extended X-ray absorption fine structure analysis. Compound 2 is only stable at cryogenic (liquid N2) temperatures, and frozen solutions as well as solid samples decompose rapidly upon warming, producing N2. However, the high-valent compound could be generated in the gas phase, and its reactivity against olefins, sulfides, and substrates with weak C–H bonds studied. Compound 2 proved to be a powerful two-electron oxidant that can add the nitrido ligand to olefin and sulfide sites as well as oxidize cyclohexadiene substrates to benzene in a formal H2-transfer process. In summary, compound 2 constitutes the first case of an octahedral FeV(N) species prepared within a neutral ligand framework and adds to the few examples of FeV species that could be spectroscopically and chemically characterized.

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Language(s): eng - English
 Dates: 2017-01-132017-06-302017-07-12
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.7b00429
 Degree: -

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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: 139 (27) Sequence Number: - Start / End Page: 9168 - 9177 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870