Light Alters the NH₃ vs N₂ H₄ Product Profile in Iron-catalyzed Nitrogen Reduction via Dual Reactivity from an Iron Hydrazido (Fe=NNH₂ ) Intermediate.

ABSTRACT: Whereas synthetically catalyzed nitrogen reduction (N₂ R) to produce ammonia is widely studied, catalysis to instead produce hydrazine (N₂ H₄ ) has received less attention despite its considerable mechanistic interest. Herein, we disclose that irradiation of a tris(phosphine)borane (P₃ ^B ) Fe catalyst, P₃ ^B Fe⁺ , significantly alters its product profile to increase N₂ H₄ versus NH₃ ; P₃ ^B Fe⁺ is otherwise known to be highly selective for NH₃ . We posit a key terminal hydrazido intermediate, P₃ ^B Fe=NNH₂ , as selectivity-determining. Whereas its singlet ground state undergoes protonation to liber

SUBMITTER: Garrido-Barros P 

PROVIDER: S-EPMC9998131 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature