Highly Selective Fe-Catalyzed Nitrogen Fixation to Hydrazine Enabled by Sm(II) Reagents with Tailored Redox Potential and pK_a.

ABSTRACT: Controlling product selectivity in multiproton, multielectron reductions of unsaturated small molecules is of fundamental interest in catalysis. For the N₂ reduction reaction (N₂RR) in particular, parameters that dictate selectivity for either the 6H⁺/6e^- product ammonia (NH₃) or the 4H⁺/4e^- product hydrazine (N₂H₄) are poorly understood. To probe this issue, we have developed conditions to invert the selectivity of a tris(phosphino)borane iron catalyst (Fe), with which NH₃ is typically the major product of N₂R, to instead favor N₂H₄ as the sole observed fixed-N product (>99:1). This dramatic shift is achieved by replacing moderate reductants

SUBMITTER: Boyd EA 

PROVIDER: S-EPMC11668122 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature