title: Isolated cationic crown ether complexes of gallium(I) and indium(I).
abstract: The recently reported homologous low-valent indium and gallium salts M(+)[Al(OR(F))(4)](-) (M = Ga, In; R(F) = C(CF(3))(3)) were used to extend the coordination chemistry of Ga(I) and In(I) to the isolated [18]crown-6 complexes [M([18]crown-6)(PhF)(2)](+)[Al(OR(F))(4)](-) in fluorobenzene solution (PhF = C(6)H(5)F). In contrast to known ion-paired compounds for M = In, our complexes are undisturbed and in the solid state free of contacts to the anion. A peculiar combination of very weak η(1)- and η(6)-coordination to the PhF-solvent was observed that allows speculation about the presence of a stereochemically active lone pair at M(I). Structure and energetics of these novel salts were rationalized on the basis of DFT calculations.
authors: Albert-Ludwigs-Universität Freiburg, Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum FMF and Freiburg Institute for Advanced Studies FRIAS, Section Soft Matter Science, Albertstr. 21, 79104 Freiburg, Germany.
authors: Alexander
authors: A
authors: Higelin
authors: Christoph
authors: C
authors: Haber
authors: Stefan
authors: S
authors: Meier
authors: Ingo
authors: I
authors: Krossing
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D043844:Crown Ethers / Q000737:chemistry*; D003460:Crystallization; D005464:Fluorobenzenes / Q000737:chemistry; D005708:Gallium / Q000737:chemistry*; D007204:Indium / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D056831:Coordination Complexes; D043844:Crown Ethers; D005464:Fluorobenzenes; D007204:Indium; D005708:Gallium