Crystal Structures of Xenon(VI) Salts: XeF₅Ni(AsF₆)₃, XeF₅AF₆ (A = Nb, Ta, Ru, Rh, Ir, Pt, Au), and XeF₅A₂F₁₁ (A = Nb, Ta)

Abstract

Experiments on the preparation of the new mixed cations XeF5M(AF6)3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF5M(SbF6)3 (M = Sn, Pb), and XeF5M(BF4)x(SbF6)3-x (x = 1, 2, 3; M = Co, Mn, Ni, Zn) salts were successful only in the preparation of XeF5Ni(AsF6)3. In other cases, mixtures of different products, mostly XeF5AF6 and XeF5A2F11 salts, were obtained. The crystal structures of XeF5Ni(AsF6)3, XeF5TaF6, XeF5RhF6, XeF5IrF6, XeF5Nb2F11, XeF5Ta2F11, and [Ni(XeF2)2](IrF6)2 were determined for the first time on single crystals at 150 K by X-ray diffraction. The crystal structures of XeF5NbF6, XeF5PtF6, XeF5RuF6, XeF5AuF6, and (Xe2F11)2(NiF6) were redetermined by the same method at 150 K. The crystal structure of XeF5RhF6 represents a new structural type in the family of XeF5AF6 salts, which crystallize in four different structural types. The XeF5A2F11 salts (M = Nb, Ta) are not isotypic and both represent a new structure type. They consist of [XeF5]+ cations and dimeric [A2F11]− anions. The crystal structure of [Ni(XeF2)2](IrF6)2 is a first example of a coordination compound in which XeF2 is coordinated to the Ni2+ cation.

Keywords

• metal
• fluorine
• xenon
• crystal structure
• Raman spectroscopy
• photochemistry