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Platinum hexafluoride is the chemical compound with the formula PtF6, and is one of seventeen known binary hexafluorides. It is a dark-red volatile solid that forms a red gas. The compound is a unique example of platinum in the +6 oxidation state. With only four d-electrons, it is paramagnetic with a triplet ground state. PtF6 is a strong fluorinating agent and one of the strongest oxidants, capable of oxidising xenon and O2. PtF6 is octahedral in both the solid state and in the gaseous state. The Pt-F bond lengths are 185 picometers.[1]

Synthesis

PtF6 was first prepared by reaction of fluorine with platinum metal.[2] This route remains the method of choice.[1]

Pt + 3 F2 → PtF6

PtF6 can also be prepared by disproportionation of the pentafluoride (PtF5), with the tetrafluoride (PtF4) as a byproduct. The required PtF5 can be obtained by fluorinating PtCl2:

2 PtCl2 + 5 F2 → 2 PtF5 + 2 Cl2
2 PtF5 → PtF6 + PtF4

Hexafluoroplatinates

Platinum hexafluoride can gain an electron to form the hexafluoroplatinate anion, PtF
6
. It is formed by reacting platinum hexafluoride with relatively uncationisable elements and compounds, for example with xenon to form "XePtF
6
" (actually a mixture of XeFPtF
5
, XeFPt
2
F
11
, and Xe
2
F
3
PtF
6
), known as xenon hexafluoroplatinate. The discovery of this reaction in 1962 proved that noble gases form chemical compounds. Previous to the experiment with xenon, PtF
6
had been shown to react with oxygen to form [O2]+[PtF6], dioxygenyl hexafluoroplatinate.

See also

References

  1. ^ a b Drews, T.; Supel, J.; Hagenbach, A.; Seppelt, K. "Solid State Molecular Structures of Transition Metal Hexafluorides" Inorganic Chemistry 2006, volume 45, pp 3782-3788.doi:10.1021/ic052029f
  2. ^ Weinstock, B.; Claassen, H. H.; Malm, J. G. (1957). "Platinum Hexafluoride". Journal of the American Chemical Society. 79 (21): 5832. doi:10.1021/ja01578a073.

General reading

  • Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.