The elusive structures of pentakis[(triphenylphosphine)gold]ammonium(2+) bis[tetrafluoroborate(1-)]

Annette Schier, Andreas Grohmann, José M. Löpez-de-Luzuriaga, Hubert Schmidbaur

Publikation: Beitrag in FachzeitschriftArtikelBegutachtung

29 Zitate (Scopus)


{Pentakis[(triphenylphosphine)gold(I)]ammonium(2+)} bis[(tetrafluoroborate)(1-)] was prepared from {tetrakis-[(triphenylphosphine)gold(I)]-ammonium(1+)} [tetrafluoroborate(1-)] and [(triphenylphosphine)gold(I)] tetrafluoroborate in hexamethyl phosphoric triamide and tetrahydrofuran at 20 °C in 53% yield and crystallized from dichloromethane as the new solvate {[(Ph3P)Au]5N}3 [BF4]6 [CH2Cl2]4. The crystal structure of this product has been determined by single-crystal X-ray methods [monoclinic, P21/n, a = 34.200(3), b = 15.285(1), c = 53.127(3) Å, β = 107.262(2)°, V = 26521(3) Å3, Z = 12, at 153 K]. The lattice contains three independent trinuclear dications that have no crystallographically imposed symmetry and are mutually similar in their molecular structure. The geometry of the [Au5N] core with pentacoordinate nitrogen atoms is intermediate between trigonal-bipyramidal and square pyramidal with severe distortions to minimize the Au-Au distances along some of the edges of the polyhedra. The three structures are thus different from that found previously in the tetrahydrofuran solvate {[(Ph3P)-Au]5N}(BF4)2(C4H8O)2, where the geometry of the same trinuclear dication is closer to the trigonal-bipyramidal reference model. The new results are discussed in the light of the structures of tetra(gold)ammonium cations in salts of the type {[(Ph3P)Au]4N}+X- and of related tetra-, penta-, and hexacoordinate poly(gold)phosphonium, -arsonium, -sulfonium, and -selenonium cations.

Seiten (von - bis)547-554
FachzeitschriftInorganic Chemistry
PublikationsstatusVeröffentlicht - 7 Feb. 2000
Extern publiziertJa


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