Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions
- 주제(키워드) C-H bond activation , DFT , nitrene transfer , oxygen atom transfer , reaction mechanism
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Li, Xiao-Xi; Lu, Xiaoyan; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Park, Jae Woo] Chungbuk Natl Univ, Dept Chem, Cheongju 28644, South Korea; [Cho, Kyung-Bin] Jeonbuk Natl Univ, Dept Chem, Jeonju 54896, South Korea
- 등재 SCIE, SCOPUS
- 발행기관 WILEY-V C H VERLAG GMBH
- 발행년도 2021
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000191129
- 본문언어 영어
- Published As https://doi.org/10.1002/chem.202103295
- PubMed https://pubmed.ncbi.nlm.nih.gov/34590742
초록/요약
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.
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