%0 Journal Article %1 https://doi.org/10.1002/anie.202103268 %A Jach, Franziska %A Wagner, Frank R. %A Amber, Zeeshan H. %A Rüsing, Michael %A Hunger, Jens %A Prots, Yurii %A Kaiser, Martin %A Bobnar, Matej %A Jesche, Anton %A Eng, Lukas M. %A Ruck, Michael %A Höhn, Peter %D 2021 %J Angew. Chem. %K a %N 29 %P 15879-15885 %R https://doi.org/10.1002/anie.202103268 %T Tricyanidoferrates(−IV) and ruthenates(−IV) with non-innocent cyanido ligands %U https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202103268 %V 60 %X Abstract Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions Fe(CN)37− and Ru(CN)37− were stabilized in LiSr3Fe(CN)3 and AE3.5M(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 LiSr3Fe(CN)3 crystallizes in P63/m, the polar space group P63 with three-fold cell volume for AE3.5M(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−)37−, quantum chemical calculations reveal non-innocent intermediate-valent CN1.67− ligands and a closed-shell d10 configuration for Fe, that is, Fe2−.

@article{https://doi.org/10.1002/anie.202103268, abstract = {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−.}, added-at = {2023-11-16T12:57:32.000+0100}, author = {Jach, Franziska and Wagner, Frank R. and Amber, Zeeshan H. and Rüsing, Michael and Hunger, Jens and Prots, Yurii and Kaiser, Martin and Bobnar, Matej and Jesche, Anton and Eng, Lukas M. and Ruck, Michael and Höhn, Peter}, biburl = {https://www.bibsonomy.org/bibtex/264b275f20b9604a92560cf09d2927f89/ctqmat}, day = 03, doi = {https://doi.org/10.1002/anie.202103268}, eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202103268}, interhash = {45f124e5ac24fb0c70d8e950d3fe989e}, intrahash = {64b275f20b9604a92560cf09d2927f89}, journal = {Angew. Chem.}, keywords = {a}, month = {05}, number = 29, pages = {15879-15885}, timestamp = {2023-11-16T12:57:32.000+0100}, title = {Tricyanidoferrates(−IV) and ruthenates(−IV) with non-innocent cyanido ligands}, url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202103268}, volume = 60, year = 2021 }