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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>