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Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions
- Title
- Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions
- Authors
- Li, Xiao-Xi; Lu, Xiaoyan; Park, Jae Woo; Cho, Kyung-Bin; Nam, Wonwoo
- Ewha Authors
- 남원우
- SCOPUS Author ID
- 남원우
- Issue Date
- 2021
- Journal Title
- CHEMISTRY-A EUROPEAN JOURNAL
- ISSN
- 0947-6539
1521-3765
- Citation
- CHEMISTRY-A EUROPEAN JOURNAL vol. 27, no. 69, pp. 17495 - 17503
- Keywords
- C-H bond activation; DFT; nitrene transfer; oxygen atom transfer; reaction mechanism
- Publisher
- WILEY-V C H VERLAG GMBH
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- 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 pi-cation radical complex, which is formally an iron(VI)-imido complex [Fe-V(NTs)(TAML(+.))] (1; NTs=tosylimido), and an iron(V)-imido complex [Fe-V(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 (FeO)-O-IV systems. This is actually in contrast to the known [Fe-V(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.
- DOI
- 10.1002/chem.202103295
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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