Ozonide ions formation

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 . 

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. 

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). 

This indicates no evidence of stereorandomization about the carbon—carbon double bond. It means that 74 cleaves in a concerted fashion to yield syn and anti zwitter-ions produced in different amounts depending on the alkene geometry. The stereo-isomeric zwitterions remain attached to each other like an ion pair and recombine stereoselectively with aldehydes. The subtle nature of ozonation, however, may be illustrated by the observation that ozonide formation may be nonconcerted under... 

The decomposition of ozone is catalyzed by the hydroxide ion. Ozone dissociates in the presence of OH to H02°/02°. Further decomposition via the ozonide anion radical 03°7 HO,° results in the formation of OH° (see Figure 2-1, Part A, p. 11). They may react with organic compounds, radical scavengers (HC03, C032-) or ozone itself. 

The double-bond character of the 9,10 bond in phenanthrene is particularly evident in ozonization. This bond is attacked preferentially, which leads to the formation of a dialdehyde when the ozonide is reduced with iodide ion ... 

Tertiary amines. Using a secondary amine to decompose an ozonide derived from 1-alkene effects its alkylation. The amine initiates an eliminative fragmentation of the ozonide to generate an aldehyde and dialkylammonium formate. Schiff base formation from the aldehyde and another molecule of the amine is then followed by reduction by the formate ion. 

The decay of the ozonide radical ion in aqueous, alkaline solution has been characterized. A complication arises from carbonate impurities in the alkaline solution, which are converted to CO3 radical ions in the pulse radiolysis experiments. The ozonide radical ion OJ (formed by reaction between 0 and O2) reacts with the carbonate radical ion to give ozone and carbonate. " This may explain why carbonate has a stabilizing effect on ozone, as both O3 and CO3 radicals have been detected during the decomposition of ozone in alkaline solutions with carbonate present, and this reaction between the two radical species may occur. The mechanism of formation of hypobromite from ozone and bromide has been studied. ... 

---