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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Prots, Yurii
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Publications (5/5 displayed)
- 2023Eu4Al13Pt9 – a coloring variant of the Ho4Ir13Ge9 type structurecitations
- 2022FeWO 4 Single Crystals: Structure, Oxidation States, and Magnetic and Transport Propertiescitations
- 2021Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non-Innocent Cyanido Ligandscitations
- 2013Cs7Nd11(SeO3)(12)Cl-16: first noncentrosymmetric structure among alkaline-metal lanthanide selenite halidescitations
- 2005Crystal structure, chemical bonding, and phase relations of the novel compound Co4Al7+xSi2-x (0.27 = x = 1.05)
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article
Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non-Innocent Cyanido Ligands
Abstract
<p>Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN)<sub>3</sub>]<sup>7−</sup> and [Ru(CN)<sub>3</sub>]<sup>7−</sup> were stabilized in LiSr<sub>3</sub>[Fe(CN)<sub>3</sub>] and AE<sub>3.5</sub>[M(CN)<sub>3</sub>] (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 LiSr<sub>3</sub>[Fe(CN)<sub>3</sub>] crystallizes in P6<sub>3</sub>/m, the polar space group P6<sub>3</sub> with three-fold cell volume for AE<sub>3.5</sub>[M(CN)<sub>3</sub>] 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<sup>−1</sup>) 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<sup>−IV</sup>(CN<sup>−</sup>)<sub>3</sub>]<sup>7−</sup>, quantum chemical calculations reveal non-innocent intermediate-valent CN<sup>1.67−</sup> ligands and a closed-shell d<sup>10</sup> configuration for Fe, that is, Fe<sup>2−</sup>.</p>