Four-Coordinate Fe N₂ and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand.

ABSTRACT: Inspired by mechanistic proposals for N₂ reduction at the nitrogenase FeMo cofactor, we report herein a new, strongly σ-donating heteroscorpionate ligand featuring two weak-field pyrazoles and an alkyl donor. This ligand supports four-coordinate Fe(I)-N₂, Fe(II)-Cl, and Fe(III)-imido complexes, which we have characterized using a variety of spectroscopic and computational methods. Structural and quantum mechanical analysis reveal the nature of the Fe-C bonds to be essentially invariant between the complexes, with conversion between the (formally) low-valent Fe-N₂ and high-valent Fe-imido complexes mediated by pyrazole hemilability. This presents a useful strategy for substrate reduction at such low-coordinate centers and suggests a mechanism by which FeMoco

SUBMITTER: McSkimming A 

PROVIDER: S-EPMC9367695 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature