The synthesis and characterization of an iron(VII) nitrido complex

Keilwerth M, Mao W, Malischewski M, Jannuzzi SA, Breitwieser K, Heinemann FW, Scheurer A, DeBeer S, Munz D, Bill E, Meyer K (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Nature Chemistry Nature Publishing Group

DOI: 10.1038/s41557-023-01418-4

Abstract

Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates in numerous catalytic processes. Structural and spectroscopic studies of well-defined model complexes often provide evidence of these intermediates. In addition to the fundamental molecular and electronic structure insights gained by these complexes, their reactivity also affects our understanding of catalytic reaction mechanisms for small molecule and bond-activation chemistry. Here, we report the synthesis, structural and spectroscopic characterization of a stable, octahedral Fe(VI) nitrido complex and an authenticated, unique Fe(VII) species, prepared by one-electron oxidation. The super-oxidized Fe(VII) nitride rearranges to an Fe(V) imide through an intramolecular amination mechanism and ligand exchange, which is characterized spectroscopically and computationally. This enables combined reactivity and stability studies on a single molecular system of a rare high-valent complex redox pair. Quantum chemical calculations complement the spectroscopic parameters and provide evidence for a diamagnetic (S = 0) d 2 Fe(VI) and a genuine S = 1/2, d 1 Fe(VII) configuration of these super-oxidized nitrido complexes. [Figure not available: see fulltext.]

Authors with CRIS profile

Martin Keilwerth Lehrstuhl für Anorganische und Allgemeine Chemie Weiqing Mao Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Andreas Scheurer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Freie Universität Berlin DE Germany (DE) Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion DE Germany (DE) Universität des Saarlandes (UdS) DE Germany (DE)

How to cite

APA:

Keilwerth, M., Mao, W., Malischewski, M., Jannuzzi, S.A., Breitwieser, K., Heinemann, F.W.,... Meyer, K. (2024). The synthesis and characterization of an iron(VII) nitrido complex. Nature Chemistry. https://doi.org/10.1038/s41557-023-01418-4

MLA:

Keilwerth, Martin, et al. "The synthesis and characterization of an iron(VII) nitrido complex." Nature Chemistry (2024).

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