Dioxygenyl hexafluoroplatinate is a

compound Compound may refer to: Architecture and built environments * Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall ** Compound (fortification), a version of the above fortified with defensive struc ...

with formula O₂PtF₆. It is a

hexafluoroplatinate A hexafluoroplatinate is a chemical compound which contains the hexafluoroplatinate anion. It is produced by combining substances with platinum hexafluoride. Examples of hexafluoroplatinates * Dioxygenyl hexafluoroplatinate (O2PtF6), containing ...

of the unusual

dioxygenyl The dioxygenyl ion, , is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of . It is formally derived from oxygen by the removal of an electron: :O2 → + e− The energy change for this process is call ...

cation, O₂⁺, and is the first known compound containing this cation. It can be produced by the reaction of

dioxygen There are several known allotropes of oxygen. The most familiar is molecular oxygen (O2), present at significant levels in Earth's atmosphere and also known as dioxygen or triplet oxygen. Another is the highly reactive ozone (O3). Others are: * ...

with

platinum hexafluoride Platinum hexafluoride is the chemical compound with the formula Pt F6, 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 sta ...

. The fact that is strong enough to oxidise , whose first

ionization potential Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule ...

is 12.2 eV, led Neil Bartlett to correctly surmise that it might be able to oxidise

xenon Xenon is a chemical element with the symbol Xe and atomic number 54. It is a dense, colorless, odorless noble gas found in Earth's atmosphere in trace amounts. Although generally unreactive, it can undergo a few chemical reactions such as the ...

(first ionization potential 12.13 eV). This led to the discovery of

xenon hexafluoroplatinate Xenon hexafluoroplatinate is the product of the reaction of platinum hexafluoride with xenon, in an experiment that proved the chemical reactivity of the noble gases. This experiment was performed by Neil Bartlett at the University of British Co ...

, which proved that the

noble gas The noble gases (historically also the inert gases; sometimes referred to as aerogens) make up a class of chemical elements with similar properties; under standard conditions, they are all odorless, colorless, monatomic gases with very low ch ...

es, previously thought to be inert, are able to form chemical compounds.

Preparation

Dioxygenyl hexafluoroplatinate can be synthesized from the elements by the action of a mixture of

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...

and

fluorine Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as a highly toxic, pale yellow diatomic gas. As the most electronegative reactive element, it is extremely reactiv ...

gas on

platinum Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Pla ...

sponge at 450 °C. It can also be prepared by the reaction of oxygen difluoride () with platinum sponge. At 350 °C,

platinum tetrafluoride Platinum tetrafluoride is the inorganic compound with the chemical formula . In the solid state, the compound features platinum(IV) in octahedral coordination geometry. Preparation The compound was first reported by Henri Moissan by the fluorinat ...

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 In geometry, a rhombohedron (also called a rhombic hexahedron or, inaccurately, a rhomboid) is a three-dimensional figure with six faces which are rhombi. It is a special case of a parallelepiped where all edges are the same length. It can be us ...

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 Tetrafluoromethane, also known as carbon tetrafluoride or R-14, is the simplest perfluorocarbon ( C F4). As its IUPAC name indicates, tetrafluoromethane is the perfluorinated counterpart to the hydrocarbon methane. It can also be classified as a ...

. 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 Potassium fluoride is the chemical compound with the formula KF. After hydrogen fluoride, KF is the primary source of the fluoride ion for applications in manufacturing and in chemistry. It is an alkali halide and occurs naturally as the rare ...

in iodine pentafluoride () solution in which

iodine heptafluoride Iodine heptafluoride, also known as iodine(VII) fluoride or iodine fluoride, is an interhalogen compound with the chemical formula I F7. It has an unusual pentagonal bipyramidal structure, as predicted by VSEPR theory. The molecule can undergo ...

is produced: :2 + 2 KF + → 2 + 2 +

References

{{oxygen compounds Fluoro complexes Oxygen compounds Platinum compounds Fluorometallates