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

Jach, Franziska; Wagner, Frank R.; Amber, Zeeshan H.; Ruesing, Michael; Hunger, Jens; Prots, Yurii; Kaiser, Martin; Bobnar, Matej; Jesche, Anton; Eng, Lukas M.; Ruck, Michael; Hoehn, Peter

doi:10.1002/anie.202103268

Item

ITEM ACTIONSEXPORT

Add to Basket

Please note that a newer version of this item is available:
https://pure.mpg.de/pubman/item/item_3327353_5

DetailsSummary

Released

Journal Article

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

MPS-Authors

/persons/resource/persons126668

Jach, Franziska
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126896

Wagner, Frank R.
Frank Wagner, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126806

Prots, Yurii
Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons146769

Bobnar, Matej
Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126823

Ruck, Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126657

Hoehn, Peter
Peter Höhn, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

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.

Cite as: https://hdl.handle.net/21.11116/0000-0008-C26C-4

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-.