4.6 Article

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

Journal

MOLECULES
Volume 28, Issue 8, Pages -

Publisher

MDPI
DOI: 10.3390/molecules28083370

Keywords

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

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Experiments on the preparation of various mixed cations salts were mostly unsuccessful, except for the successful preparation of XeF5Ni(AsF6)(3). Crystal structures were determined for several salts, including XeF5Ni(AsF6)(3), XeF5TaF6, XeF5RhF6, XeF5IrF6, XeF5Nb2F11, XeF5Ta2F11, and [Ni(XeF2)(2)](IrF6)(2).
Experiments on the preparation of the new mixed cations XeF5M(AF(6))(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 XeF(5)AF(6) and XeF(5)A(2)F(11) 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 XeF(5)AF(6) salts, which crystallize in four different structural types. The XeF(5)A(2)F(11) salts (M = Nb, Ta) are not isotypic and both represent a new structure type. They consist of [XeF5](+) cations and dimeric [A(2)F(11)](-) 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.

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