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However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe<jats:sup>II<\/jats:sup> and Fe<jats:sup>III<\/jats:sup> precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV\u2010visible, M\u00f6ssbauer), ESI\u2010MS and DFT studies, an Fe<jats:sup>IV<\/jats:sup> tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe<jats:sup>II<\/jats:sup> precursor was expected by a two\u2010electron oxidative addition, its formation from an Fe<jats:sup>III<\/jats:sup> precursor was unprecedented. Thanks to a combination of spectroscopic (UV\u2010visible, EPR, Hyscore and M\u00f6ssbauer), ESI\u2010MS and DFT studies, we found that, when starting from the Fe<jats:sup>III<\/jats:sup> precursor, an Fe<jats:sup>III<\/jats:sup> tosyliodinane adduct was formed and decomposed into an Fe<jats:sup>V<\/jats:sup> tosylimido species which generated the catalytically active Fe<jats:sup>IV<\/jats:sup> tosylimide through a comproportionation process with the Fe<jats:sup>III<\/jats:sup> precursor.<\/jats:p>","DOI":"10.1002\/chem.202201875","type":"journal-article","created":{"date-parts":[[2022,9,21]],"date-time":"2022-09-21T09:44:48Z","timestamp":1663753488000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Catalytic Nitrene Transfer by an Fe<sup>IV<\/sup>\u2010Imido Complex Generated by a Comproportionation Process"],"prefix":"10.1002","volume":"28","author":[{"given":"Jordan","family":"Donat","sequence":"first","affiliation":[{"name":"Univ. 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