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

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2022 Jul 27

PMID 35895990

Authors

Alex McSkimming

Niklas B Thompson

Affiliations

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Abstract

Inspired by mechanistic proposals for N 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)-N, 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-N 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 might accommodate the binding of both π-acidic and π-basic nitrogenous substrates.

Citing Articles

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