From Zintl to Wade: Ba3LiGa5 – A Structure Pattern with Pyramidal Cluster Chains –[Ga5]n–. Issue 29 (29th June 2020)

• Record Type: Journal Article
• Authors: Kotsch, Matthias; Prots, Yurii; Ormeci, Alim; Bobnar, Matej; Wagner, Frank R.; Senyshyn, Anatoliy; Grin, Yuri
• Is Part Of: European journal of inorganic chemistry. Issue 29(2020)
• Page Start: 2842
• Page End: 2849
• Publication Date: 2020-06-29
• Subjects: Intermetallic phases -- Clusters compounds -- Zintl phases -- NMR spectroscopy -- Neutron diffraction; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000413
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Investigation of the correlation between the crystal structure, electronegativity difference and valence electron concentration in intermetallic gallides lead to the discovery of the new compound Ba3 LiGa5 (space group Immm, a = 6.2720(2) Å, b = 6.5872(2) Å, c = 12.6878(8) Å). A combination of quantum chemical bonding analysis with NMR study revealed the gallium substructure to be formed of chains built of the interconnected pyramidal [Ga5 ] clusters. Analysis of chemical bonding by means of the electron localizability approach confirmed the presence nido ‐[Ga5 ] Wade clusters. Lithium species are not only required for the purpose of charge compensation, but also – analogous to a transition metal – occupies partially the same crystallographic position as gallium. Abstract : The new compound Ba3 LiGa5 is the first known one in the ternary Ba–Li–Ga system. It can be best described by means of the nido –[Ga5 ] cluster poly‐anion with Ba and Li cationic counterparts. Their interaction within the gallium poly‐anion is multi–atomic and strongly polar. Lithium plays a dual role in Ba3 LiGa5 : on the one hand, it bodies for the charge compensation, and on the other one, it substitutes gallium at the same crystallographic position, thus behaving rather as a transition metal.