Platinum hexafluoride

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]

Platinum hexafluoride
Names
IUPAC name
Platinum(VI) fluoride
Other names
Platinum hexafluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.816
EC Number
  • 237-214-0
  • InChI=1S/6FH.Pt/h6*1H;/q;;;;;;+2/p-6 checkY
    Key: NHVLQWBIZQMDAU-UHFFFAOYSA-H checkY
  • InChI=1S/6FH.Pt/h6*1H;/q;;;;;;+2/p-6
  • Key: NHVLQWBIZQMDAU-UHFFFAOYSA-H
  • F[Pt](F)(F)(F)(F)F
Properties
PtF6
Molar mass 309.07 g/mol
Appearance dark-red crystals
Density 3.83 g/cm3
Melting point 61.3 °C (142.3 °F; 334.4 K)
Boiling point 69.14 °C (156.45 °F; 342.29 K)
Reacts with water
Structure
Orthorhombic, oP28
Pnma, No. 62
octahedral (Oh)
0
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Strong oxidizer
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
4
0
3
OX
Related compounds
Related compounds
 Platinum(IV) fluoride
Platinum(V) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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
2F
11, and Xe
2F
3PtF
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. 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.
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