Between imide, imidyl and nitrene - an imido iron complex in two oxidation states

Reith S, Demeshko S, Battistella B, Reckziegel A, Schneider C, Stoy A, Lichtenberg C, Meyer F, Munz D, Werncke CG (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Chemical Science Royal Society of Chemistry

DOI: 10.1039/d2sc01088g

Abstract

Imidyl and nitrene metal species play an important role in the N-functionalisation of unreactive C-H bonds as well as the aziridination of olefines. We report on the synthesis of the trigonal imido iron complexes [Fe(NMes)L2]^0,− (L = -N{Dipp}SiMe3); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl) via reaction of mesityl azide (MesN3) with the linear iron precursors [FeL2]^0,−. UV-vis-, EPR-, ⁵⁷Fe Mössbauer spectroscopy, magnetometry, and computational methods suggest for the reduced form an electronic structure as a ferromagnetically coupled iron(ii) imidyl radical, whereas oxidation leads to mixed iron(iii) imidyl and electrophilic iron(ii) nitrene character. Reactivity studies show that both complexes are capable of H atom abstraction from C-H bonds. Further, the reduced form [Fe(NMes)L2]⁻ reacts nucleophilically with CS2 by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L2] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.

Authors with CRIS profile

Dominik Munz Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Philipps-Universität Marburg

Germany (DE) Georg-August-Universität Göttingen

Germany (DE) Humboldt-Universität zu Berlin

Germany (DE)

How to cite

APA:

Reith, S., Demeshko, S., Battistella, B., Reckziegel, A., Schneider, C., Stoy, A.,... Werncke, C.G. (2022). Between imide, imidyl and nitrene - an imido iron complex in two oxidation states. Chemical Science. https://dx.doi.org/10.1039/d2sc01088g

MLA:

Reith, Sascha, et al. "Between imide, imidyl and nitrene - an imido iron complex in two oxidation states." Chemical Science (2022).

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