Dioxygenyl hexafluoroplatinate

Preparation

Dioxygenyl hexafluoroplatinate can be synthesized from the elements by the action of a mixture of oxygen and fluorine gas on platinum sponge at 450 °C. It can also be prepared by the reaction of oxygen difluoride () with platinum sponge. At 350 °C, platinum tetrafluoride is produced; above 400 °C, dioxygenyl hexafluoroplatinate is formed.

:T = 350 °C: 2 + Pt → +

:T 400 °C: 6 + 2 Pt → 2 +

Bartlett demonstrated that it can be synthesized at room temperature by the reaction of oxygen gas with .

:O2 + PtF6 → O2PtF6

Structure

Dioxygenyl hexafluoroplatinate(V) has a rhombohedral crystal structure at low temperatures, and a cubic structure at high temperatures, isomorphous to potassium hexafluoroplatinate(V), . Its ionic lattice is indicated by its insolubility in carbon tetrafluoride. In its cubic form, the octahedra are slightly compressed along the three-fold rotational axis, along which the long axis of the cations also lies. Each cation is surrounded by 12 fluorine atoms, 6 of which surround it in a puckered six-membered ring, and of the remaining 3 each belong to the two octahedra lying along the long axis of the cation.

Reactions

Dioxygenyl hexafluoroplatinate(V) is a convenient route to prepare other platinum(V) compounds, such as potassium hexafluoroplatinate(V) via reaction with potassium fluoride in iodine pentafluoride () solution in which iodine heptafluoride is produced:

:2 + 2 KF + → 2 + 2 +

References

References

1. Bartlett, Neil. (1962). "Xenon hexafluoroplatinate(V), {{chem". [[Proc. Chem. Soc.]].
2. (1962). "Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), {{chem". [[J. Chem. Soc.]].
3. (1967). "Halogen Chemistry". [[Academic Press]].