Between imide, imidyl and nitrene – an imido iron complex in two oxidation states
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Philipps-Universität Marburg
Abstract
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively
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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