Kinetics and mechanisms of oxidations by metal ions. Part 17. Oxidation of formate ion by alkaline osmium tetroxide
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Summary
The oxidation of formate ion by alkaline osmium tetroxide, such that [HCO inf2 p− ] ≫ [OsVII], exhibits first-order dependence in [OsVII], an order less than unity in [HCO inf2 p− ], and zero-order in [OH−]. HCO2− reacts as an ion-pair formed with an alkali metal ion and [OsO4(OH)2]2− is the reactive species of OsVII. The formation of an intermediate OsVII-HCO2M complex is substantiated by the rapid-scan spectra of the reaction mixture. Anions (Cl−, ClO inf4 p− ) have no effect on the rate. The close agreement between the observed kH/kD = 7.1 and the theoretically calculated value (7.0), based on the stretching frequencies of C-H and C-D bonds in the free molecule, indicates an outer-sphere mechanism.
Keywords
Oxidation Physical Chemistry Inorganic Chemistry Alkali Metal Osmium
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