Concerning the nature of XePtF₆

Interaction of PtF₆ vapor with a comparable molar quantity of Xe gas, at ≈ 20⁰C, gives a sticky, red-tinged yellow solid of composition Xe(PtF₆)_x, with 1 ≤ x ≤ 2, X-ray powder diffraction pattern (XRDP) of which show the presence of XeF⁺PtF₆ ^- {a =8.081(6); b = 11.087(7); c = 7.226(6) Å; β= 90.01(5)°; VIZ = 161.8(4) ų} which is isostructural with XeF₊RuF₆ ^-. This implies that first formed XePtF₆ + PtF₆ → XeF⁺PtF₆ ^- + PtF₅ (non-crystalline). When the product having x ≈ 2 is warmed (≤ 60°C) it is converted to the orange-red, friable solid XeF⁺Pt₂Fn₁₁ ^-: XeF₊PtF₆ ^- + PtF₅ → XeF⁺Pt₂F₁₁ ^-. Mixing PtF₆ vapor (diluted with SF₆ gas), with a large excess of Xe gas, with the product mixture quenched at 77 K, gives a mustard yellow solid of composition ≈ XePtF₆. This does not give an XRDP, and is only weakly paramagnetic. Dissolution of PtF₄, with a large excess of XeF₂ in aHF gives a yellow solution, the ¹⁹F NMR spectrum of which reveals PtF₆ ^2-. The diamagnetic, amorphous, aHF-insoluble solid, of composition ≈ XePtF₆ obtained from that solution is probably a XeF⁺ salt of polymeric (PtF₅ ^-)_n. The 1:1 product of Xe + PtF₆ is also likely to be of this formulation.