Dioxygen difluoride is a compound of fluorine and oxygen with the molecular formula O2F2. It can exist as an orange-colored solid which melts into a red liquid at . It is an extremely strong oxidant and decomposes into oxygen and fluorine even at at a rate of 4% per dayits lifetime at room temperature is thus extremely short. Dioxygen difluoride reacts vigorously with nearly every chemical it encounters (including ordinary ice) leading to its onomatopoeic nickname FOOF (a play on its chemical structure and its explosive tendencies). Dioxygen difluoride can be obtained by subjecting a 1:1 mixture of gaseous fluorine and oxygen at low pressure (7–17 mmHg (0.9–2.3 kPa) is optimal) to an electric discharge of 25–30 mA at 2.1–2.4 kV. A similar method was used for the first synthesis by Otto Ruff in 1933. Another synthesis involves mixing O2 and F2 in a stainless steel vessel cooled to , followed by exposing the elements to 3MeV bremsstrahlung for several hours. A third method requires heating a mix of fluorine and oxygen to , and then rapidly cooling it using liquid oxygen. All of these methods involve synthesis according to the equation O2 + F2 → O2F2 It also arises from the thermal decomposition of ozone difluoride: 2 O3F2 → 2 O2F2 + O2 In O2F2, oxygen is assigned the unusual oxidation state of +1. In most of its other compounds, oxygen has an oxidation state of −2. The structure of dioxygen difluoride resembles that of hydrogen peroxide, H2O2, in its large dihedral angle, which approaches 90° and C2 symmetry. This geometry conforms with the predictions of VSEPR theory. The bonding within dioxygen difluoride has been the subject of considerable speculation, particularly because of the very short O−O distance and the long O−F distances. The O−O bond length is within 2 pm of the 120.7 pm distance for the O=O double bond in the dioxygen molecule, O2. Several bonding systems have been proposed to explain this, including an O−O triple bond with O−F single bonds destabilised and lengthened by repulsion between the lone pairs on the fluorine atoms and the π orbitals of the O−O bond.
Yves Pilloud, Ruud van Heeswijk
Paul Joseph Dyson, Ning Yan, Xiao Yuan