ISSN:
1572-901X
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
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 k H/k D = 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00167032
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