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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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 Creators:
Jach, Franziska1, Author              
Wagner, Frank R.2, Author              
Amber, Zeeshan H.3, Author
Ruesing, Michael3, Author
Hunger, Jens3, Author
Prots, Yurii4, Author              
Kaiser, Martin3, Author
Bobnar, Matej1, Author              
Jesche, Anton3, Author
Eng, Lukas M.3, Author
Ruck, Michael5, Author              
Hoehn, Peter6, Author              
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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 Abstract: 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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Language(s): eng - English
 Dates: 2021-05-032021-05-03
 Publication Status: Published in print
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 Table of Contents: -
 Rev. Type: -
 Identifiers: ISI: 000661723900001
DOI: 10.1002/anie.202103268
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Title: Angewandte Chemie, International Edition in English
  Abbreviation : Angew. Chem., Int. Ed. Engl.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 60 (29) Sequence Number: - Start / End Page: 15879 - 15885 Identifier: ISSN: 0570-0833
CoNE: https://pure.mpg.de/cone/journals/resource/0570-0833