Hydrazine, Azides, Hydroxylamines, and Derivatives

Diphasic kinetics are observed in the oxidation of hydrazoic acid by bis(2,2 -bipyridine)manganese(III) ions. ° Analysis of the kinetics suggests that both [Mn(bpy)2N3] and [Mn(bpy)2N3] are involved in the oxidation process producing free radicals, N3. The diazido salt cw-[Co(en)2(N3)2] is reduced by Fe(II) in acidic solution.The kinetics may be explained by an inner-sphere mechanism utilizing the azide ions as bridges. 

Iron is found to catalyze the reduction of peroxide-bound chromium(IV) by hydroxylamine in acetate buffered media. The proposed catalytic sequence involves recycling of dissolved iron between the 4-2 and 4-3 states, the rapid oxidation of Fe(II) by Cr(IV) (fc = 3 x 10 M s ), a rate-determining one-electron oxidation of Fe(III)-bound NH30H ion by Cr(IV), and the rapid reaction of Fe(III)(ONNH2) with excess NH30H. The kinetics of oxidation of HONH2-HC1 by chloramine-B in HCl medium have been reported.  

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