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

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 P6₃ /m, the polar space group P6₃ 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 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 CN^1.67- ligands and a closed-shell d¹⁰ configuration for Fe, that is, Fe^2- .

SUBMITTER: Jach F

PROVIDER: S-EPMC8362014 | biostudies-literature |

REPOSITORIES: biostudies-literature

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