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  2,3,5,6-Tetrafluorophenylnitren-4-yl:  Electron Paramagnetic Resonance Spectroscopic Characterization of a Quartet-Ground-State Nitreno Radical

Sander, W., Grote, D., Kossmann, S., & Neese, F. (2008). 2,3,5,6-Tetrafluorophenylnitren-4-yl:  Electron Paramagnetic Resonance Spectroscopic Characterization of a Quartet-Ground-State Nitreno Radical. Journal of the American Chemical Society, 130(13), 4396-4403. doi:10.1021/ja078171s.

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 Urheber:
Sander, Wolfram1, Autor
Grote, Dirk1, Autor
Kossmann, Simone2, Autor
Neese, Frank2, Autor           
Affiliations:
1Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, D-44780 Bochum, Germany, ou_persistent22              
2Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              

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 Zusammenfassung: 2,3,5,6-Tetrafluorophenylnitren-4-yl (5) was synthesized in argon at 4 K via the photolysis of 2,3,5,6-tetrafluoro-4-iodo-phenyl azide (6). Electron paramagnetic resonance (EPR) spectroscopy allows us to observe triradical 5 in its quartet state with the zero-field splitting (ZFS) parameters |D/hc| = 0.285 and |E/hc| = 0.043 cm-1. The quartet ground state of 5 is in accordance with our previous infrared (IR) spectroscopic investigation, in which the high-spin quartet state, but no low-spin doublet state, of 5 was observed in solid argon at 4 K [Wenk, H. H.; Sander, W. Angew. Chem., Int. Ed.2002, 41, 2742−2745]. Because annealing of the matrix at temperatures of >10 K results in the rapid recombination of the highly reactive species 5 with I atoms produced during the photolysis of 6, the Curie−Weiss behavior could not be investigated. However, the absence of low-spin states in the IR investigations, as well as the results of ab initio and density functional theory (DFT) calculations, strongly suggest that 5 has a robust quartet ground state that is best-described as an unprecedented σ,σ,π-triradical. The ZFS of 5 has been successfully reproduced by DFT calculations, which furthermore provide qualitative insight into the origin of the observed EPR parameters.

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Sprache(n): eng - English
 Datum: 2007-10-252008-03-082008-04-01
 Publikationsstatus: Erschienen
 Seiten: 8
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ja078171s
 Art des Abschluß: -

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Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 130 (13) Artikelnummer: - Start- / Endseite: 4396 - 4403 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870