Mechanism of the reduction of molecular nitrogen to hydrazine by niobium (iii) hydroxide

The effect of the concentration of water on the rate of reduction of molecular nitrogen to hydrazine by niobium(iii) hydroxide in alkaline H₂O−MeOH and D₂O−MeOD mixtures was studied. In both cases, the reaction rate is maximum when H₂O]=4 mol L⁻¹, and the inverse isotopic effect (K ^D/k ^H>1) is observed when H₂O]<20 mol L⁻¹. Similar regularity was observed for the reaction of hydrogen elimination. It was found that HD is formed in the H₂O−MeOH system in the presence of D₂. The conclusion was made that the ratedetermining stage in hydrazine formation is the transfer of a hydride ion to the dinitrogen molecule coordinated to the binuclear Nb^III center. A kinetic scheme satisfactorily explaining the effect of the concentration of water (H₂O]=1.5−49.0 mol L⁻¹) on the reaction rate constant was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1600–1604, September, 1997.