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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 ¼ –N{Dipp}SiMe3); Dipp ¼ 2,6-diisopropyl-phenyl; Mes ¼ (2,4,6-trimethylphenyl) via
reaction of mesityl azide (MesN3) with the linear iron precursors [FeL2]0,-. UV-vis-, EPR-, 57Fe M¨ossbauer
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.
Reith, Sascha (0000-0002-2747-0809); Demeshko, Serhiy; Battistella, Beatrice (0000-0002-5963-3684); Reckziegel, Alexander; Schneider, Christian (0000-0001-5291-3010); Stoy, Andreas; Lichtenberg, Crispin (0000-0002-0176-0939); Meyer, Franc (0000-0002-8613-7862); Munz, Dominik (0000-0003-3412-651X); Werncke, C. Gunnar (0000-0002-9963-8391): Between imide, imidyl and nitrene – an imido iron complex in two oxidation states. In: , Jg. (2022-07-18), . DOI: https://doi.org/10.17192/es2022.0101.
