Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands
F. Jach, F.R. Wagner, Z.H. Amber, M. Rüsing, J. Hunger, Y. Prots, M. Kaiser, M. Bobnar, A. Jesche, L.M. Eng, M. Ruck, P. Höhn, Angewandte Chemie International Edition 60 (2021) 15879–15885.
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Journal Article
| Published
| English
Author
Jach, Franziska;
Wagner, Frank R.;
Amber, Zeeshan H.;
Rüsing, MichaelLibreCat 
;
Hunger, Jens;
Prots, Yurii;
Kaiser, Martin;
Bobnar, Matej;
Jesche, Anton;
Eng, Lukas M.;
Ruck, Michael;
Höhn, Peter
All
;
Hunger, Jens;
Prots, Yurii;
Kaiser, Martin;
Bobnar, Matej;
Jesche, Anton;
Eng, Lukas M.;
Ruck, Michael;
Höhn, Peter
All
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 AE3.5[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 P63/m, the polar space group P63 with three-fold cell volume for AE3.5[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 π-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 d10 configuration for Fe, that is, Fe2−.
Keywords
Publishing Year
Journal Title
Angewandte Chemie International Edition
Volume
60
Issue
29
Page
15879-15885
LibreCat-ID
Cite this
Jach F, Wagner FR, Amber ZH, et al. Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands. Angewandte Chemie International Edition. 2021;60(29):15879-15885. doi:10.1002/anie.202103268
Jach, F., Wagner, F. R., Amber, Z. H., Rüsing, M., Hunger, J., Prots, Y., Kaiser, M., Bobnar, M., Jesche, A., Eng, L. M., Ruck, M., & Höhn, P. (2021). Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands. Angewandte Chemie International Edition, 60(29), 15879–15885. https://doi.org/10.1002/anie.202103268
@article{Jach_Wagner_Amber_Rüsing_Hunger_Prots_Kaiser_Bobnar_Jesche_Eng_et al._2021, title={Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands}, volume={60}, DOI={10.1002/anie.202103268}, number={29}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Jach, Franziska and Wagner, Frank R. and Amber, Zeeshan H. and Rüsing, Michael and Hunger, Jens and Prots, Yurii and Kaiser, Martin and Bobnar, Matej and Jesche, Anton and Eng, Lukas M. and et al.}, year={2021}, pages={15879–15885} }
Jach, Franziska, Frank R. Wagner, Zeeshan H. Amber, Michael Rüsing, Jens Hunger, Yurii Prots, Martin Kaiser, et al. “Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands.” Angewandte Chemie International Edition 60, no. 29 (2021): 15879–85. https://doi.org/10.1002/anie.202103268.
F. Jach et al., “Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands,” Angewandte Chemie International Edition, vol. 60, no. 29, pp. 15879–15885, 2021, doi: 10.1002/anie.202103268.
Jach, Franziska, et al. “Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands.” Angewandte Chemie International Edition, vol. 60, no. 29, Wiley, 2021, pp. 15879–85, doi:10.1002/anie.202103268.
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