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)L
2]
0,− (L = –N{Dipp}SiMe
3); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl)
via reaction of mesityl azide (MesN
3) with the linear iron precursors [FeL
2]
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)L
2]
− reacts nucleophilically with CS
2 by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L
2] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.A pair of trigonal imido iron complexes ([Fe(NMes)L
2]
0,−) in two oxidation states is reported. The anionic complex K{crypt.222}[Fe(NMes)L
2] is best described as an iron(
ii) imide.
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