Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions

Xiao Xi Li, Xiaoyan Lu, Jae Woo Park, Kyung Bin Cho, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


High-valent iron-imido complexes can perform C−H activation and sulfimidation reactions, but are far less studied than the more ubiquitous iron-oxo species. As case studies, we have looked at a recently published iron(V)-imido ligand π-cation radical complex, which is formally an iron(VI)-imido complex [FeV(NTs)(TAML+.)] (1; NTs=tosylimido), and an iron(V)-imido complex [FeV(NTs)(TAML)] (2). Using a theoretical approach, we found that they have multiple energetically close-lying electromers, sometimes even without changing spin states, reminiscent of the so-called Compound I in Cytochrome P450. When studying their reactivity theoretically, it is indeed found that their electronic structures may change to perform efficient oxidations, emulating the multi-spin state reactivity in FeIVO systems. This is actually in contrast to the known [FeV(O)(TAML)] species (3), where the reactions occur only on the ground spin state. We also looked into the whole reaction pathway for the C−H bond activation of 1,4-cyclohexadiene by these intermediates to reproduce the experimentally observed products, including steps that usually attract no interest (neither theoretically nor experimentally) due to their non-rate-limiting status and fast reactivity. A new “clustering non-rebound mechanism” is presented for this C−H activation reaction.

Original languageEnglish
Pages (from-to)17495-17503
Number of pages9
JournalChemistry - A European Journal
Issue number69
StatePublished - 9 Dec 2021

Bibliographical note

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© 2021 Wiley-VCH GmbH


  • C−H bond activation
  • DFT
  • nitrene transfer
  • oxygen atom transfer
  • reaction mechanism


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