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|Title: ||Kinetics and mechanism of uncatalyzed oxidation of hydrazine with superoxide coordinated to cobalt(III)|
|Authors: ||Mondal, Amit|
|Issue Date: ||May-2009|
|Series/Report no.: ||Int. Cl.8 CO7B33/00|
|Abstract: || Hydrazine, in deoxygenated aqueous solutions at moderate pH 3.8-6.1, quantitatively reduces [(NH3)5CoIII( μ-superoxo)CoIII(NH3)5]5+ (I) to the corresponding peroxo complex, [(NH3)5CoIII(μ-peroxo)CoIII(NH3)5]4+ (II) which, instead of reacting with another molecule of hydrazine quickly decomposes to Co2+ according to the overall stoichiometry: 4(I) + N2H5+ + 35H+ = 8Co2+ + 40NH4+ + N2 + 4O2. The reaction is dramatically catalyzed by Cu2+, to the degree that impurity levels of Cu2+ are sufficient to mask the direct reaction such that the direct oxidation process is inaccessible, though the reaction is not catalyzed by any of the other usual transition metal centers. Dipicolinic acid is a very effective inhibitor of this trace metal ion catalysis, and with 0.10 mM dipicolinic acid, the direct oxidation can be studied, which reveals an inverse [H+] dependence of reaction rate for the direct reaction. This has been ascribed to the formation of a conjugate base, [(NH3)4(NH2)CoIII(μ-superoxo)CoIII(NH3)5]4+ as the kinetically active species. Change in buffer concentration has no effect on the rate, neither is there any observable kinetic solvent isotope effect. Enthalpy of activation has a moderate value while the entropy of activation is moderately negative. A reaction scheme consistent with these kinetic and stoichiometric observations has been proposed. |
|Appears in Collections:||IJC-A Vol.48A(05) [May 2009]|
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