Ozonide ions reactions

The ozonides are characterized by the presence of the ozonide ion, O - They are generally produced by the reaction of the inorganic oxide and ozone (qv). Two reviews of ozonide chemistry are available (1,117). Sodium ozonide [12058-54-7] NaO potassium ozonide [12030-89-6] 35 rubidium ozonide [12060-04-7] RbO and cesium ozonide [12053-67-7] CsO, have all been reported (1). Ammonium ozonide [12161 -20-5] NH O, and tetramethylammonium ozonide [78657-29-1/, (CH ) NO, have been prepared at low temperatures (118). 

The ozonide ion has widely spaced energy levels, and to first order the g values are not influenced by the host lattice or the surface. Thus, the absolute values of the g values are useful in the identification of the ion. These g values, along with the hyperfine coupling constants, are given in Table I. The three sets of hyperfine constants indicate that the oxygen atoms are not equivalent, at least when the ozonide ion is formed according to reaction 2. The geometry of the ion on MgO is believed to be... 

Reactions of 07 with Alkanes and Alkenes. Ozonide ions are intermediate in reactivity between 0 and 01 (20,21). On MgO they re-... 

The formation of similar reaction products when alkanes react with either 0 or 07 suggests that the ozonide ion may first dissociate according to the reverse of reaction 2, and the alkane would then react with the 0 ion. However, the lifetime for the 07 ion under vacuum is considerably longer than the lifetime for the reaction of 07 with an alkane. In addition, each alkane reacts with 07 at a characteristic rate therefore, it seems likely that the alkane reacts directly with 07> rather than indirectly with 0 . 

Alkanes—Continued reactions—Continued with ozonide ions, 135 with superoxide ions, 134-35 role of oxygen ions in oxidation. 138-41 Alkenes, reactions with oxygen ions, 134 with ozonide ions, 135 with superoxide ions, 134-35 Aluminosilicate gels, alkali cations, 241... 

However, it must be borne in mind that in previous work, H2 did not react with a triangular array of O ions to form OH" ions (354). If such a reaction with H2 occurred, then the O" ions would no longer be available for Oj formation. Moreover, the reaction of pairs of O ions with oxygen should lead to pairs of O J ions which would have an abnormal EPR spectrum if they can be seen at all. In fact, the g tensor is as expected for isolated OJ ions. The CoO-MgO system behaves as CaO for the formation of Oj, i.e., via invisible O ions. The ozonide ions characterized by a three-g-value EPR signal (2.0025, 2.012, 2.017) do not exhibit any superhyperfine interaction with cobalt nuclei, suggesting that they are adsorbed on Mg2+ ions (110). Depending on the system (MgO, CaO, CoO-MgO) and the experimental conditions, the ozonide ion Oj disappears irreversibly between 25° and 130°C. In the case of MgO (333,334), OJ ions are formed when O J ions are destroyed, whereas for CaO (158) and CoO-MgO (110) the evidence is not clear. 

The Ozonide Ion.—The red crystalline substance potassium ozonide, KO3, is obtained by recrystallizing from liquid ammonia the product of reaction of ozone and potassium hydroxide.47 The corresponding ozonides NaO and CsO hasre been shown48 to have magnetic susceptibility corresponding to the presence of the OjT ion with one odd electron. The electronic structure of the ozonide ion is... 

The ozonide ion is paramagnetic with one unpaired electron and is apparently bent ( 100° O—O 1.2A) (cf. C102). There is evidence that 03 occurs as a reaction intermediate in the decomposition of H202 in alkaline solution24 and in radiolytic reactions.25... 

High-temperature molecules like lithium fluoride (LiF) can be trapped in matrices by evaporating the molecule from the crystalline solid in a Knudsen cell at high temperature or by reacting lithium atoms with fluorine molecules during condensation. The latter method has been used to synthesize the calcium oxide (CaO) molecule from the calcium atom-ozone reaction, which gives the calcium ozonide ion pair Ca 03 and CaO diatomic products. 

Ozonation ofAlkenes. The most common ozone reaction involves the cleavage of olefinic carbon—carbon double bonds. Electrophilic attack by ozone on carbon—carbon double bonds is concerted and stereospecific (54). The modified three-step Criegee mechanism involves a 1,3-dipolar cycloaddition of ozone to an olefinic double bond via a transitory TT-complex (3) to form an initial unstable ozonide, a 1,2,3-trioxolane or molozonide (4), where R is hydrogen or alkyl. The molozonide rearranges via a 1,3-cycloreversion to a carbonyl fragment (5) and a peroxidic dipolar ion or zwitterion (6). 

Holcman, J., K. Sehested, E. Bjergbakke, and E. J. Hart, Formation of Ozone in the Reaction between the Ozonide Radical Ion, 02, and the Carbonate Radial Ion, CO, in Aqueous Alkaline Solutions, J. Phys. Chem., 86, 2069-2072 (1982). 

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