Ge24− Dumbbells with Very Short Ge−Ge Distances in the Zintl Phase Li3NaGe2: A Solid-State Equivalent to Molecular O2Report as inadecuate


Ge24− Dumbbells with Very Short Ge−Ge Distances in the Zintl Phase Li3NaGe2: A Solid-State Equivalent to Molecular O2


Ge24− Dumbbells with Very Short Ge−Ge Distances in the Zintl Phase Li3NaGe2: A Solid-State Equivalent to Molecular O2 - Download this document for free, or read online. Document in PDF available to download.

Publication Date: 2015-12-02

Journal Title: Angewandte Chemie International Edition

Publisher: Wiley

Volume: 128

Issue: 3

Pages: 1087-1091

Language: English

Type: Article

Metadata: Show full item record

Citation: Scherf, L. M., Karttunen, A. J., Pecher, O., Magusin, P. C. M. M., Grey, C. P., & Fässler, T. F. (2015). [Ge2]4− Dumbbells with Very Short Ge−Ge Distances in the Zintl Phase Li3NaGe2: A Solid-State Equivalent to Molecular O2. Angewandte Chemie International Edition, 128 (3), 1087-1091.

Description: This is the accepted manuscript. The final version is available at http://onlinelibrary.wiley.com/wol1/doi/10.1002/ange.201508044/abstract.

Abstract: The novel ternary Zintl phase Li3NaGe2 comprises alkali-metal cations and [Ge2]4− dumbbells. The diatomic [Ge2]4− unit is characterized by the shortest Ge−Ge distance (2.390(1) Å) ever observed in a Zintl phase and thus represents the first Ge=Ge double bond under such conditions, as also suggested by the (8−N) rule. Raman measurements support these findings. The multiple-bond character is confirmed by electronic-structure calculations, and an upfield 6Li NMR shift of −10.0 ppm, which was assigned to the Li cations surrounded by the π systems of three Ge dumbbells, further underlines this interpretation. For the unperturbed, ligand-free dumbbell in Li3NaGe2, the π- bonding py and pz orbitals are degenerate as in molecular oxygen, which has singly occupied orbitals. The partially filled π-type bands of the neat solid Li3NaGe2 cross the Fermi level, resulting in metallic properties. Li3NaGe2 was synthesized from the elements as well as from binary reactants and subsequently characterized crystallographically.

Keywords: Doppelbindungen, Germanium, Lithium, Natrium, Zintl-Phasen

Sponsorship: O.P. acknowledges support from a Marie Skłodowska-Curie Individual Fellowship. L.M.S. is further grateful to the Fonds der Chemischen Industrie and the Studienstiftung des deutschen Volkes for her fellowships. A.J.K. gratefully acknowledges funding from the Alfred Kordelin Foundation and computational resources from CSC – the Finnish IT Center for Science.

Identifiers:

This record's URL: http://dx.doi.org/10.1002/ange.201508044https://www.repository.cam.ac.uk/handle/1810/254024





Author: Scherf, Lavinia M.Karttunen, Antti J.Pecher, OliverMagusin, Pieter C. M. M.Grey, Clare P.Fässler, Thomas F.

Source: https://www.repository.cam.ac.uk/handle/1810/254024



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