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

Autor: Jach F; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.; Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany., Wagner FR; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany., Amber ZH; Institute of Applied Physics, Technische Universität Dresden, 01062, Dresden, Germany., Rüsing M; Institute of Applied Physics, Technische Universität Dresden, 01062, Dresden, Germany., Hunger J; Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany., Prots Y; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany., Kaiser M; Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany., Bobnar M; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.; current address: J. Stefan Institute, Jamova 39, 1000, Ljubljana, Slovenia., Jesche A; Institute of Physics, University of Augsburg, Universitätsstrasse 1, 86159, Augsburg, Germany., Eng LM; Institute of Applied Physics, Technische Universität Dresden, 01062, Dresden, Germany.; Würzburg-Dresden Cluster of Excellence ct.qmat, Technische Universität Dresden, 01062, Dresden, Germany., Ruck M; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.; Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.; Würzburg-Dresden Cluster of Excellence ct.qmat, Technische Universität Dresden, 01062, Dresden, Germany., Höhn P; Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Jul 12; Vol. 60 (29), pp. 15879-15885. Date of Electronic Publication: 2021 Jun 15.
DOI: 10.1002/anie.202103268
Abstrakt: Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN) 3 ] 7- and [Ru(CN) 3 ] 7- were stabilized in LiSr 3 [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 LiSr 3 [Fe(CN) 3 ] crystallizes in P6 3 /m, the polar space group P6 3 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 d 10 configuration for Fe, that is, Fe 2- .
(© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: