Theoretical insights into the reduction reaction of Np(VI) by tert-butylhydrazine

Tert-butylhydrazine ((CH₃)₃CN₂H₃) is a potential reductant with exceptional selectivity for the reduction of Np(VI), yet the reduction mechanism of Np(VI) with (CH₃)₃CN₂H₃ remains unclear. Herein, we explored the reduction reaction of Np(VI) with (CH₃)₃CN₂H₃ using scalar-relativistic density functional theory. We found that the first Np(VI) reduction in pathway I and the second Np(VI) reduction in pathway III is kinetically optimal among three pathways I–III. The reduction nature of Np(VI) is revealed by the bond distance of Np-O_yl and spin density of Np. This work theoretically expands the understanding of Np(VI) reduction with hydrazine derivatives.

The reduction reaction of Np(VI) by (CH₃)₃CN₂H₃ molecule was investigated by scalar-relativistic DFT calculations, where the first and second Np(VI) reduction can be ascribed to outer-sphere electron transfer and hydrogen transfer, respectively.