Terminal N₂ Dissociation in [(PNN)Fe(N₂ )]₂ (μ-N₂ ) Leads to Local Spin-State Changes and Augmented Bridging N₂ Activation.

ABSTRACT: Nitrogen fixation at iron centres is a fundamental catalytic step for N₂ utilisation, relevant to biological (nitrogenase) and industrial (Haber-Bosch) processes. This step is coupled with important electronic structure changes which are currently poorly understood. We show here for the first time that terminal dinitrogen dissociation from iron complexes that coordinate N₂ in a terminal and bridging fashion leaves the Fe-N₂ -Fe unit intact but significantly enhances the degree of N₂ activation (Δν≈180 cm^-1 , Raman spectroscopy) through charge redistribution. The transformation proceeds with local spin state change at the iron centre (S= 1/2${{ 1/2 }}$ →S=³ /₂ ). Further dissociation of the bridging N₂ c

SUBMITTER: Regenauer NI 

PROVIDER: S-EPMC9804668 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature