Coordination Chemistry of Copper and Nickel with Xenon Difluoride and the Hexafluororuthenate(V) Anion: Synthesis and Structural Studies
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M(RuF6)2 (M = Cu, Ni) are synthesized from MF2, F2, and Ru under UV light. Different amounts of XeF2 are added to the salt. In the reactions between M(RuF6)2 and 2XeF2, the compounds [M(XeF2)2](RuF6)2 (M = Cu, Ni) are formed. Their crystal structures are isotypic. However, when reacted with an excess of XeF2, the compounds [M(XeF2)6](RuF6)2 (M = Cu, Ni) are obtained.
In the photochemical reactions between MF2 (M = Cu, Ni), Ru, and F2 in anhydrous HF, Cu(RuF6)2, and Ni(RuF6)2 are formed. Only crystals of Cu(RuF6)2 are obtained during the crystallization of the powdered products. Cu(RuF6)2 crystallizes in the triclinic space group P1¯$\bar{1}$. The Cu atoms are coordinated by six F atoms, which are shared with octahedral RuF6 units. Together, they form slabs that are interconnected by van der Waals forces. In the reactions between M(RuF6)2 (M = Cu, Ni) and 2XeF2 (1:2 molar ratio), [Cu(XeF2)2](RuF6)2 and [Ni(XeF2)2](RuF6)2 are formed. They both crystallize in the monoclinic space group P21/c. The metal center is coordinated by six F atoms. Two F atoms are provided by two nonbridging XeF2 molecules, while the remaining four originate from four bridging [RuF6]- anions. In the reactions between M(RuF6)2 (M = Cu, Ni) and an excess of XeF2, [Cu(XeF2)6](RuF6)2 and [Ni(XeF2)6](RuF6)2 are formed. They are not isostructural, as the first crystallizes in the triclinic space group P1¯$\bar{1}$, while the second crystallizes in the trigonal space group R3¯$\bar{3}$. In both cases, homoleptic cations [M(XeF2)6]2+ are present, with the metal center coordinated by six nonbridging XeF2 molecules, while the [RuF6]- anions are discrete.
