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Titel:Between imide, imidyl and nitrene – an imido iron complex in two oxidation states
Autor:Reith, Sascha
Weitere Verfasser:Demeshko, Serhiy; Battistella, Beatrice; Reckziegel, Alexander; Schneider, Christian; Stoy, Andreas; Lichtenberg, Crispin; Meyer, Franc; Munz, Dominik; Werncke, C. Gunnar
URN: urn:nbn:de:hebis:04-es2022-01011
DDC:540 Chemie


iron imide electronic structure

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.

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