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  Tricyanidoferrates(-IV) and Ruthenates(-IV) with Non-Innocent Cyanido Ligands

Jach, F., Wagner, F. R., Amber, Z. H., Ruesing, M., Hunger, J., Prots, Y., et al. (2021). Tricyanidoferrates(-IV) and Ruthenates(-IV) with Non-Innocent Cyanido Ligands. Angewandte Chemie, International Edition in English, 60(29), 15879-15885. doi:10.1002/anie.202103268.

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Jach, Franziska1, Autor           
Wagner, Frank R.2, Autor           
Amber, Zeeshan H.3, Autor
Ruesing, Michael3, Autor
Hunger, Jens3, Autor
Prots, Yurii4, Autor           
Kaiser, Martin3, Autor
Bobnar, Matej1, Autor           
Jesche, Anton3, Autor
Eng, Lukas M.3, Autor
Ruck, Michael5, Autor           
Hoehn, Peter6, Autor           
Affiliations:
1Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863405              
2Frank Wagner, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863409              
3External Organizations, ou_persistent22              
4Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863424              
5Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863444              
6Peter Höhn, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863419              

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 Zusammenfassung: Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN)(3)](7-) and [Ru(CN)(3)](7-) were stabilized in LiSr3[Fe(CN)(3)] and AE(3.5)[M(CN)(3)] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of -IV. Microcrystalline powders were obtained by a solid-state route, single crystals from alkali metal flux. While LiSr3[Fe(CN)(3)] crystallizes in P6(3)/m, the polar space group P6(3) with three-fold cell volume for AE(3.5)[M(CN)(3)] is confirmed by second harmonic generation. X-ray diffraction, IR and Raman spectroscopy reveal longer C-N distances (124-128 pm) and much lower stretching frequencies (1484-1634 cm(-1)) than in classical cyanidometalates. Weak C-N bonds in combination with strong M-C pi-bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe-IV(CN-)(3)](7-), quantum chemical calculations reveal non-innocent intermediate-valent CN1.67- ligands and a closed-shell d(10) configuration for Fe, that is, Fe2-.

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Sprache(n): eng - English
 Datum: 2021-05-032021-05-03
 Publikationsstatus: Erschienen
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 Art der Begutachtung: -
 Identifikatoren: ISI: 000661723900001
DOI: 10.1002/anie.202103268
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Titel: Angewandte Chemie, International Edition in English
  Kurztitel : Angew. Chem., Int. Ed. Engl.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Weinheim : Wiley-VCH
Seiten: - Band / Heft: 60 (29) Artikelnummer: - Start- / Endseite: 15879 - 15885 Identifikator: ISSN: 0570-0833
CoNE: https://pure.mpg.de/cone/journals/resource/0570-0833