Why Do Five Ga+ Cations Form a Ligand‐Stabilized [Ga5]5+ Pentagon and How Does a 5:1 Salt Pack in the Solid State?. (28th August 2019)

• Record Type: Journal Article
• Authors: Glootz, Kim; Himmel, Daniel; Kratzert, Daniel; Butschke, Burkhard; Scherer, Harald; Krossing, Ingo
• Is Part Of: Angewandte Chemie. Volume 131:Number 40(2019)
• Page Start: 14300
• Page End: 14304
• Publication Date: 2019-08-28
• Subjects: Dichtefunktionaltheorie -- Galliumkationen -- Hauptgruppenchemie -- Kationische Cluster -- Schwach koordinierende Anionen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201907974
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The reaction of the Ga + source [Ga(PhF)2 ] + [Al(OR F )4 ] − with the neutral σ‐donor ligand dmap (4‐Me2 N‐C6 H4 N) produces the unexpectedly large and fivefold positively charged cluster cation salt [Ga5 (dmap)10 ] 5+ ([Al(OR F )4 ] − )5 . It includes a regular and planar Ga5 pentagon with strong metal–metal bonding. Additionally, the compound represents the first salt in which an ionic 1:5 packing is realized. We discuss the nature of this structure which results from the conversion of the non‐bonding 4s 2 lone‐pair orbitals into fully Ga‐Ga‐bonding orbitals and the solid‐state arrangement of the ions constituting the lattice as an almost orthohexagonal AX5 lattice, possibly the aristotype of any 5:1 salt. Abstract : Geschichten über Pentakationen : Mithilfe des starken σ‐Donors 4‐Dimethylaminopyridin (dmap) erhalten Ga + ‐Ionen genug Elektronendichte, um ihre nichtbindenden 4s 2 ‐Orbitale in bindende Ga‐Ga‐Molekülorbitale umzuwandeln und zu aggregieren. Als Resultat bildet sich das pentagonale Pentakation [Ga5 (dmap)10 ] 5+ . Es kristallisiert mit dem Gegenion [Al(OR F )4 ] − in einem fast orthohexagonalen AX5 ‐Gitter, was möglicherweise der Aristotyp aller 5:1‐Salze ist.