3,385,666 United States Patent 0 " ice Patented May 28, 1968 1 2 of novel compositions that can be used as a source of 3,385,666 both ozone and oxygen. DIOXYGENYL FLUORIDES OF GROUP V An additional object of this invention is the preparation ELEMENTS of the nitronium ion and intermediates for preparing Archie R. Young II, Montclair, Tetsuyuki Hirata, Whar novel nitronium salts. ton, and Scott I. Morrow, Morris Plains, N.J., assign Further objects of this invention will become apparent ors to Thiokol Chemical Corporation, Bristol, Pa., a corporation of Delaware to the reader upon a further reading of this patent appli No Drawing. Filed Jan. 6, 1964, Ser. No. 336,061 cation. 11 Claims. (Cl. 23-203) The above objects among many others are achieved by 10 the direct interaction of certain ?uoride reactants with This invention relates to a novel class of ?uorinated, dioxygen di?uoride at reaction temperatures well below oxygen containing, oxidizing agents and to a process for 0° C. As indicated earlier the ?uoride reactant is selected their preparation. from the group consisting of Group V ?uorides. More particularly, this invention concerns the prepara The preferred practice is to contact the ?uoride reactant tion of certain stable ?uorides of the cationic dioxygenyl 15 with an excess of 02112 at low temperatures ranging from radical. These novel-oxidizing agents have the formula: —l60 to \—78° C. until a substantial amount of prod uct is formed. The product is isolated after evacuating off the excess 021:2, ?uorine and gaseous by-products. wherein (O2) is the dioxygenyl radical having a charge In one ‘favored process embodiment of this invention of +1, M is an element selected from the group consist 20 a ?uoride reactant chosen ‘from the preferred phosphorus, ing of phosphorus, arsenic antimony and bismuth. arsenic and antimony ?uoride reactants are reacted with The novel compounds of this invention have utility as an excess of O2F2 until the desired product is formed. For oxidizing agents, particularly in aqueous environments. example an illustration embodiment of the preferred proc The reaction of the inventive dioxygenyl ?uorides with ess is to contact AsF5 ‘with an excess of 02132 (the O2F2 water is as follows: 25 is generated by passing a 10,000 volt D.C. discharge through an equimolar mixture of O2 and F2 maintained at 20 mm. pressure and —196° C. temperature) until a wherein M is a Group V element selected from the ele substantial quantity of product is formed. The end point ments consisting of P, As, Sb, and Bi. of the reaction and the course of the reaction can be fol Because of the concurrent liberation of both 02 and 30 lowed by the disappearance of the orange color of the 03 as typi?ed by the reaction of the Group V dioxygenyl O2F2 reactant, as well as by measuring the free ?uorine ?uorides with water, the novel compositions have applica evolved during the reaction. tion for a variety of oxidizing uses. For example, the com In another preferred process embodiment of this in positions of this invention can be used as additives or vention, SbF5 is contacted with an excess of O2F2 pre components in solid and liquid *bleaches for both industrial 35 pared as described above until visual appearance indicate and household application. the formation of the O2SbF6 product. The product can be In addition, these novel dioxygenyl compounds can be isolated after evacuating the excess 021-72 from the system. used to produce the powerful oxidizer the nitronium ion In yet another preferred embodiment of this invention from nitrogen dioxide. For example, the arsenic com PF5 is contacted with an excess of 02132 prepared by the pound oxidizes NO2 as follows: 40 described gaseous discharge method at about —165° C. until the dissipation of the orange color of the 0J3 indicates that a reaction has taken place. Again evacuation The novel compounds of this invention are both unusual of the system is a convenient means of isolating and puri and advantageous in several respects. For example, the fying the product. compositions represent a novel and relatively stabilized 45 In' yet another preferred embodiment, BiF5 is reacted form of the dioxygenyl cation (02+). While a synthesis with excess 021:2 gas at temperatures below —160° C. un of the dioxygenyl platinum hexa?uoride has been recently til it appear as though the reaction is completed. These reported in Proc. Chem. Soc., p. 115 (1962) the method of preferred embodiments of the invention involving the preparation described in the pulbication differs substan preparation of the Group V ?uorides of the dioxygen cat tially from the method used in this inventive process. In 50 ion are described in greater detail in the examples of this fact the published process used to prepare the prior art application which follow infra. compounds cannot be used to prepare the compounds of As indicated supra the process of this invention can be this invention but is limited exclusively to ?uorides such as used to prepare dioxygenyl ?uoride salts generally. In the PtFs and RhF6 that are exceedingly powerful oxidizing generic process the dioxygenyl ?uoride reactant in excess agents. 55 is contacted with a source of the desired ?uoride cation at With the above unusual characteristics and uses in the low temperatures described earlier until the orange mind, it is an object of this invention among others to color of the 02132 is dissipated to produce the desired prepare stable, heretofore unreported salts of the di product. ‘ oxygenyl [02+] cation by the reaction of dioxygen di As indicated by the illustrative process embodiments ?uoride with the simple ?uorides of the elements of 60 described above, there is considerable latitude in so far Group V of the Periodic Table. as reaction conditions and reactants and the ratio of re Another object of this invention is to prepare novel actants are concerned. For example, while the reaction and potent oxidizing agents useful for a variety of pur should preferably be run at temperatures below or about poses. the melting point of 021:2 (—160° C.) a somewhat A further object of this invention is to prepare a group 65 broader temperature range (-l60° C. to ---78"‘) can be 3,385,666 3 4 used. Under the conditions of temperatures and pressure Table I which follows gives the X-ray diffraction pat favored the reaction is substantially completed within 3 terns of the product. hours after the reactants are brought together. However depending upon the individual reactants and temperatures TABLE I.—DIFFRA‘CTI-ON PATTERNS OF O2As'F6 employed the reaction time can be extended or reduced 5 Cubic Unit Cell a6=8.00:l:.02 A. ()zAsFn considerably. h, k, l d, A. (Caled.) d, A. I/Ig (ReL) The ratio of the two reactants is not critical to the op 111 4. 62 4. 60 100 erability of the process. However, especially favorable re 200 4. 0O 3. 99 100 sults have been obtained when a large excess of the 220 2. 83 2. 83 50 311 2. 41 2. 43 10 dioxygendi?uoride over the stoichiometric equimolar 10 222 2. 31 2. 32 20 ratios are used and for this reason a large excess of this ..... _ _ _ _ _ _ 2. 10 5 reactant is preferred. 400 2. 00 2. 01 10 _____ - _ . _ _ _ 1. 93 4 The novel dioxygenated salts of this invention are white 331 1. 83 1. 85 10 420 1. 79 1. 80 20 to yellowish white solids at room temperature. The phos 422 1. 63 1. 64 20 phorus compound is fairly stable at room temperature 15 333, 511 1. 54 1. 55 15 _____ __ - . _ - 1. 49 6 but can be stored at lower temperatures (below —80° C.) 440 1. 42 1. 42 6 without signi?cant degradation for long periods of time. 531 1. 35 1. 36 10 442, 600 1. 33 1. 34 10 The anhydrous arsenic and antimony compounds are 620 1. 27 1. 27 5 stable for periods of up to several weeks at room tempera 533 1.22 ____ ---- ture. Mass spectral evidence indicates that all of the 20 Group V compounds decompose upon heating as follows: Example 3.—Preparation of O2SbF6 wherein M is an element selected from Group V of the The preparation of 02SbF6 is carried out using a ?uoro plastic and brass apparatus similar to the all glass ap Periodic Table. 25 Infrared spectra taken on the compounds show absorp paratus described in Example I. A 5 millimole portion of tions due to the anions MFG. SbF5 is weighed into the ?uoroplastic tube in an inert The dioxygen-di?uoride reactant is prepared by the dis nitrogen atmosphere. The ?uoroplastic tube is attached charge method of Kirschenbaum and Grosse, J .A.C.S. 81, to the vacuum system proximate to the 02132 reactant generated by electrical discharge at -196° C., the gen 1277 (1959). The P, As, Sb, and Bi penta?uorides are 30 known chemicals of commerce. erated 02132 is warmed to —80° C. and vacuum distilled Further advantages and uses of the inventive composi into the plastic tube containing the SbF5 reactant kept at tions are shown by the illustrative examples which follow: ~196° C. The reaction mixture is warmed to —80° C. at which temperature the dioxygenditluoride melts and ?ows Example 1.——Preparation of OZPFG onto the solid antimony penta?uoride. The O2SbF6 is A 0.5 millimole of PF5 is condensed as a white solid on pumped under vacuum for 7 hours and stored under dry the bottom of an all glass vacuum apparatus kept at nitrogen at room temperature.