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

Jach F, Wagner FR, Amber ZH, Ruesing M, Hunger J, Prots Y, Kaiser M, Bobnar M, Jesche A, Eng LM, Ruck M, Hoehn P (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 60

Pages Range: 15879-15885

Journal Issue: 29

DOI: 10.1002/anie.202103268

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−.

Involved external institutions

Universität Augsburg DE Germany (DE) Max-Planck-Institut für Chemische Physik fester Stoffe (MPI CPfS) / Max Planck Institute for Chemical Physics of Solids DE Germany (DE) Technische Universität Dresden DE Germany (DE)

How to cite

APA:

Jach, F., Wagner, F.R., Amber, Z.H., Ruesing, M., Hunger, J., Prots, Y.,... Hoehn, 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

MLA:

Jach, Franziska, et al. "Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non-Innocent Cyanido Ligands." Angewandte Chemie International Edition 60.29 (2021): 15879-15885.

BibTeX: Download