Hydrazine, Azide, Hydroxylamine, and Derivatives

Electron transfer between hydrazine and methyl-substituted hydrazines and the cyano complexes of Fe(III), Mo(V), and W(V) in aqueous media proceed via an outer-sphere mechanism. The rate data obtained are consistent with the Marcus theory. The reactions are pH dependent with a rate law shown in equation 

The reaction between HN3 and [Mn(bipy)2(H20) ] was followed spec-trophotometrically at 400 nm. The reaction shows an initial increase in absorbance followed by a decrease to zero, which may be explained by the formation of two 1 1 complexes with NJ. Both these complexes, [Mn(bipy)2(N3)] and [Mn(bipy)2(OH)(N3)], are involved in the oxidation process, producing N3 free radicals. The oxidation stoichiometry confirms the overall reaction as in equation 

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