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Why Do Five Ga⁺ Cations Form a Ligand-Stabilized [Ga₅ ]⁵⁺ Pentagon and How Does a 5:1 Salt Pack in the Solid State?

ABSTRACT: The reaction of the Ga⁺ source [Ga(PhF)₂ ]⁺ [Al(OR^F )₄ ]^- with the neutral ?-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 4s² 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.

SUBMITTER: Glootz K

PROVIDER: S-EPMC6790617 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Why Do Five Ga+ Cations Form a Ligand-Stabilized [Ga5 ]5+ Pentagon and How Does a 5:1 Salt Pack in the Solid State?

Glootz Kim K Himmel Daniel D Kratzert Daniel D Butschke Burkhard B Scherer Harald H Krossing Ingo I

Angewandte Chemie (International ed. in English) 20190828 40

The reaction of the Ga+ source [Ga(PhF)2 ]+ [Al(ORF )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(ORF )4 ]- )5 . It includes a regular and planar Ga5 pentagon with strong metal-metal bonding. ...[more]

PMID: 31369694

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