Dioxygenyl hexafluoroantimonate

Stein, L., Removal of Xenon and Radon from Contaminated Atmospheres with Dioxygenyl Hexafluoroantimonate, O SbF, Nature 243, No. 5401, 30-32 (May 4, 1973). 

Dioxygenyl hexafluoroantimonate has been studied by differential thermal analysis.864 Decomposition of 02+SbF,s proceeds in two stages, according to the mechanism given in Eqs. (4.217) and (4.218). 

One-electron oxidants convert tertiary amines into aminium ions. Chlorine dioxide is an example of such a reagent this converts triethylamine and other tertiary alkylamines into aminium ions, which normally react further by the loss of hydrogen from an a-carbon atom. An example of a synthetic (plication of this reaction sequence is shown in Scheme 24, the inteimediate iminium ion being intercepted intramolecularly." Nitrosonium tetrafluoroborate and dioxygenyl hexafluoroantimonate, 02 SbF6, are also good one-electron oxidants which can be used at low temperature." ... 

The C)2 1 Sh2I i i was converted to 02+SbI fi by heating at 130°C in vacuo conversely, 02+Sb2Fn- was prepared by reaction of 02 1 SbFfi and SbF5 at 180-200°C. Dioxygenyl hexafluoroarsenate is markedly less stable than the hexafluoroantimonate salts it decomposes rapidly at 130-180°C. 02 1 PtF(, can be sublimed above 90°C in vacuo and melts with some decomposition at 219°C in a sealed tube.863... 

This trigonal distortion of the MFg ion is similar to that previously observed in the rhombohedral potassium hexafluoro-osmate(v) structured Each ion has twelve fluorine neighbours, six in a puckered ring and almost coplanar with the ion, the other six in sets of three, one above and one below this plane. The situation of the dioxygenyl ion with its long axis coincident with the three-fold rotation axis is more acceptable on the grounds of close packing than the alternative random orientation (equivalent to rotation) of the ion. Apart from the non-spherical nature of the cation, the structure is almost identical with that proposed for the potassium hexafluoroantimonate(v). ... 

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