Issue 26, 2022

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

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.

Graphical abstract: Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Febr. 2022
Accepted
28 Maijs 2022
First published
09 Jūn. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 7907-7913

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

S. Reith, S. Demeshko, B. Battistella, A. Reckziegel, C. Schneider, A. Stoy, C. Lichtenberg, F. Meyer, D. Munz and C. G. Werncke, Chem. Sci., 2022, 13, 7907 DOI: 10.1039/D2SC01088G

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