Kinetics and mechanisms of oxidations by metal ions. Part 17. Oxidation of formate ion by alkaline osmium tetroxide |
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Authors: | Minakshi Vishnoi Aditya Prakash Raj N Mehrotra |
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Institution: | (1) Department of Chemistry, J.N.V. University, 342005 Jodhpur, India |
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Abstract: | 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.Author to whom all correspondence should be directed. |
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Keywords: | |
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