Dioxygenyl salt

The hexafluoroplatinate(V) anion was first obtained (58) as the dioxygenyl salt, [O2] [PtFe], by the action of an oxygen-fluorine mixture on platinum... 

Palladium(V) and palladium(III) complexes have also been reported. Two complexes of palladium(V) have been isolated (02)[PdF6] and Na[PdF6]. These were formed by the oxidation of PdF4 in HF with KrF2 in the presence of 02 and NaF respectively.3 The dioxygenyl salt may also be prepared by the reaction of palladium powder with an F2/02 mixture at 320 °C and 60 000 psi. The Raman spectrum of [PdF6] is comparable with other MF6 ions, showing bands for Vi, v2 and v3 at 643, 570 and 268 cm-1. 

The few dioxygenyl salts described in the literature require the preparation of some highly unstable fluorinating agents, such as... 

A simple synthesis of these salts became available with the recognition that oxygen, fluorine, and arsenic or antimony-(V) fluoride, at pressures near atmospheric, react to form the appropriate dioxygenyl salts when exposed to ordinary sunlight Filtered by Pyrex glass.4 Thus, the atmospheric-pressure, photochemical synthesis is the safest and most convenient one to date. 

Several interesting rearrangements (stereomutations) were observed for a series of l-anisyl-2-vinylcyclopropanes (32, Ar = CgH -OCty. These reorganizations have been elaborated in greater detail than most other radical cation reactions. For this reason, we will consider them in somewhat greater detail, even though they were initiated primarily by chemical, rather than photochemical electron transfer. Treatment of the m-isomer (cis-32) with aminium or dioxygenyl salts at... 

A series of dioxygenyl salts of complex fluorometallates, including the new 02 -[RhF6], has been simply prepared by static heating of the metal at 300—350 °C with 5 atm of a 3 1 mixture of fluorine and oxygen.90 The deep red Rh species was characterized by correlating X-ray diffraction, Raman, and mass spectral data with analogous known systems. 

Hatinum( v)-—Twelve dioxygenyl salts of complex fluorometallate anions, [MF6] (M = As, Sb, Bi, Ru, Rh, Au, or Pt) have been prepared by static heating of the metal at 300—350°C with 5 atm of 3 1 fluorine-oxygen mixture for upwards of 10 h.193 The salts were characterized by powder X-ray, Raman, and mass spectroscopy. 

It now appears that the dioxygenyl salt 02 BF4 may have been prepared prior to 1962 (36), although the nature of the material was not elucidated. This and other interesting related work was reviewed in 1966 (36) with extensive reference to sources that are not readily available in the literature. Several Og salts have now been prepared (see Table III) (37-43). In addition, there is a preliminary report of the preparation of VFg by the reaction of OgFa and VFg... 

Dioxygenyl Salts Oa SbFs" and 02 Sb2Fu" and Their Convenient Laboratory Syntheses... 

All manipulations were carried out in Kel-F, Teflon FEP, or fused silica reaction vessels attached to a stainless steel or Monel fluorine-type vacuum system and/or in a Vacuum Atmospheres inert atmosphere Dri lab. Hexafluorobenzme, oclafluorotoluene, octafluoronaphthalene (PCR Inc., Gainesville, FL), sulfur dioxide, anhydrous hydrogen fluoride (Matheson, E. Rutherford, NJ), cesium fluoride (ROC/RIC, Sun Valley, CA), trifluoroacetic acid (Aldrich, Milwaukee, Wl), and tungsten hexafluoride, arsenic pentafluoride, and antimony pentafluoride (Ozark-Mahoning, Inc., Tulsa, OK) were used as received after their purity was checked by infrared spectroscopy. Dioxygenyl salts and rhenium and... 

The magnetic susceptibility of NO- -[PtFj]" (cub.) has been measured over the temperature range 77—303° k. As in the case of the dioxygenyl salt,i the susceptibility obeys the Curie-Weiss law (6 being NOPtF, 32 0,PtF, 45°). This simple behaviour shows that there are no strong interactions of the molecular magnets and in view of the isomorphism and near isodimensionality of the two salts, the susceptibility of the [PtF,] ion has been taken to be the sttme in both. The molar... 

D. E. McKee and N. Bartlett, Dioxygenyl Salts OjSbFg and OjSb ... 

The formation of O2F3 has been suggested to explain the reaction of OFg with Lewis acids (SbFg, AsFg) giving dioxygenyl salts. The reaction was observed [1], and it has been proposed... 

BF3 reacts with O2F2 at low temperatures to give the dioxygenyl salt O2BF4 [29, 36, 38, 39]. The reaction is complete within 10 min at 147 K [36]. 

The reaction with O2 may lead to the formation of O4F [18], see also Fluorine Suppl. Vol. 2, 1980, p. 139. An equilibrium O2F + n02 (02)n+iF was Indicated by ESR studies of the reaction chemistry of dioxygenyl salts and may be responsible for the frequently observed blue<->violet color change [2]. 

The reaction O2F + F2- 02F2+ F was part of a chain mechanism explaining the fast rate of the photochemical synthesis of dioxygenyl salts from O2-F2-MF5 mixtures (M = As, Sb) [9]. The reactions with Br2 and I2 lead to chemiluminescence from electronically excited BrF and IF... 

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