Dioxygenyl hexafluoroplatinate

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Dioxygenyl hexafluoroplatinate
Dioxygenyl-3DV-vdW.svg
Platinum-hexafluoride-3D-vdW.png
Names
IUPAC name
Dioxygenyl hexafluoroplatinate
Other names
Dioxygenyl hexafluoroplatinate(V)
Identifiers
3D model (JSmol)
  • InChI=1S/6FH.O2.Pt/c;;;;;;1-2;/h6*1H;;/q;;;;;;+1;+5/p-6
    Key: VUKFIJBZILBYOF-UHFFFAOYSA-H
  • O=[O+].F[Pt-](F)(F)(F)(F)F
Properties
F6O2Pt
Molar mass 341.072 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Dioxygenyl hexafluoroplatinate is a compound with formula O2PtF6. It is a hexafluoroplatinate of the unusual dioxygenyl cation, O2+, and is the first known compound containing this cation. [1] It can be produced by the reaction of dioxygen with platinum hexafluoride. The fact that PtF
6
is strong enough to oxidise O
2
, whose first ionization potential is 12.2  eV, led Neil Bartlett to correctly surmise that it might be able to oxidise xenon (first ionization potential 12.13 eV). This led to the discovery of xenon hexafluoroplatinate, [2] which proved that the noble gases, previously thought to be inert, are able to form chemical compounds.

Contents

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. [1] It can also be prepared by the reaction of oxygen difluoride (OF
2
) with platinum sponge. At 350 °C, platinum tetrafluoride is produced; above 400 °C, dioxygenyl hexafluoroplatinate is formed. [1]

T = 350 °C:    2 OF
2
  +   Pt   PtF
4
  +  O
2
T > 400 °C:    6 OF
2
  +   2 Pt    2 O
2
PtF
6
  +  O
2

Bartlett demonstrated that it can be synthesized at room temperature by the reaction of oxygen gas with PtF
6
. [1]

O2  +   PtF6   O2PtF6

Structure

Dioxygenyl hexafluoroplatinate(V) has a rhombohedral crystal structure at low temperatures, and a cubic structure at high temperatures, [3] isomorphous to potassium hexafluoroplatinate(V), KPtF
6
. Its ionic lattice is indicated by its insolubility in carbon tetrafluoride. In its cubic form, the PtF
6
octahedra are slightly compressed along the three-fold rotational axis, along which the long axis of the [O
2
]+
cations also lies. Each O+
2
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 PtF
6
octahedra lying along the long axis of the cation. [1]

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 (IF
5
) solution [3] in which iodine heptafluoride is produced:

2 O
2
PtF
6
  +   2 KF   +  IF
5
   2 KPtF
6
  +   2 O
2
  +  IF
7

Related Research Articles

<span class="mw-page-title-main">Xenon hexafluoroplatinate</span> Chemical compound

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 Columbia, who formulated the product as "Xe+[PtF6]", although subsequent work suggests that Bartlett's product was probably a salt mixture and did not in fact contain this specific salt.

In chemistry, noble gas compounds are chemical compounds that include an element from the noble gases, group 18 of the periodic table. Although the noble gases are generally unreactive elements, many such compounds have been observed, particularly involving the element xenon.

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Iodine heptafluoride is an interhalogen compound with the chemical formula IF7. It has an unusual pentagonal bipyramidal structure, with D5h symmetry, as predicted by VSEPR theory. The molecule can undergo a pseudorotational rearrangement called the Bartell mechanism, which is like the Berry mechanism but for a heptacoordinated system.

<span class="mw-page-title-main">Xenon tetrafluoride</span> Chemical compound

Xenon tetrafluoride is a chemical compound with chemical formula XeF
4
. It was the first discovered binary compound of a noble gas. It is produced by the chemical reaction of xenon with fluorine:

<span class="mw-page-title-main">Xenon hexafluoride</span> Chemical compound

Xenon hexafluoride is a noble gas compound with the formula XeF6. It is one of the three binary fluorides of xenon that have been studied experimentally, the other two being XeF2 and XeF4. All known are exergonic and stable at normal temperatures. XeF6 is the strongest fluorinating agent of the series. It is a colorless solid that readily sublimes into intensely yellow vapors.

<span class="mw-page-title-main">Platinum hexafluoride</span> Chemical compound

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.

<span class="mw-page-title-main">Xenon difluoride</span> Chemical compound

Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2
, and one of the most stable xenon compounds. Like most covalent inorganic fluorides it is moisture-sensitive. It decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.

Xenon compounds are compounds containing the element xenon (Xe). After Neil Bartlett's discovery in 1962 that xenon can form chemical compounds, a large number of xenon compounds have been discovered and described. Almost all known xenon compounds contain the electronegative atoms fluorine or oxygen. The chemistry of xenon in each oxidation state is analogous to that of the neighboring element iodine in the immediately lower oxidation state.

<span class="mw-page-title-main">Xenon oxytetrafluoride</span> Chemical compound

Xenon oxytetrafluoride is an inorganic chemical compound. It is an unstable colorless liquid with a melting point of −46.2 °C that can be synthesized by partial hydrolysis of XeF
6
, or the reaction of XeF
6
with silica or NaNO
3
:

<span class="mw-page-title-main">Gold(V) fluoride</span> Chemical compound

Gold(V) fluoride is the inorganic compound with the formula Au2F10. This fluoride compound features gold in its highest known oxidation state. This red solid dissolves in hydrogen fluoride but these solutions decompose, liberating fluorine.

<span class="mw-page-title-main">Dioxygenyl</span> Chemical compound

The dioxygenyl ion, O+
2
, is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of +1/2. It is formally derived from oxygen by the removal of an electron:

<span class="mw-page-title-main">Manganese(IV) fluoride</span> Chemical compound

Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is a powerful oxidizing agent and is used as a means of purifying elemental fluorine.

<span class="mw-page-title-main">Oxygen compounds</span> Different oxidation states of Oxygen

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −12 (superoxides), −13 (ozonides), 0, +12 (dioxygenyl), +1, and +2.

A hexafluoride is a chemical compound with the general formula QXnF6, QXnF6m−, or QXnF6m+. Many molecules fit this formula. An important hexafluoride is hexafluorosilicic acid (H2SiF6), which is a byproduct of the mining of phosphate rock. In the nuclear industry, uranium hexafluoride (UF6) is an important intermediate in the purification of this element.

<span class="mw-page-title-main">Hexafluoroplatinate</span>

A hexafluoroplatinate is a chemical compound which contains the hexafluoroplatinate PtF−6 anion. It is produced by combining substances with platinum hexafluoride.

Chromium pentafluoride is the inorganic compound with the chemical formula CrF5. It is a red volatile solid that melts at 34 °C. It is the highest known chromium fluoride, since the hypothetical chromium hexafluoride has not yet been synthesized.

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A hypothetical chemical compound is a chemical compound that has been conceived of, but is not known to have been synthesized, observed, or isolated.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

Nickel tetrafluoride is an inorganic compound with a chemical formula NiF4.

References

  1. 1 2 3 4 5 Bartlett, Neil; Lohmann, D. H. (1962). "Fluorides of the Noble Metals. Part II. Dioxygenyl hexafluoroplatinate(V), [O
    2
    ]+
    [PtF
    6
    ]
    ". J. Chem. Soc. 115: 5253–5261. doi:10.1039/jr9620005253.
  2. Bartlett, Neil (1962). "Xenon hexafluoroplatinate(V), Xe+
    [PtF
    6
    ]
    ". Proc. Chem. Soc. : 197–236. doi:10.1039/PS9620000197.
  3. 1 2 Beveridge, A. D.; Clark, H. C. (1967). "Pentahalides of the Transition Metals". In Gutmann, Viktor (ed.). Halogen Chemistry. Vol. 3. Academic Press. pp. 179–226. ISBN   9780323148474.