Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism
- 등재 SCIE, SCOPUS
- 발행기관 American Chemical Society
- 발행년도 2017
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000145620
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.7b03310
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such complexes and related oxidation mechanism are still unsolved after decades of experimental efforts. Density functional calculations were employed to explore the structure-reactivity relationship of the iron(III)-iodosylbenzene complex, [FeIII(tpena-) (PhIO)]2+ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic structures (a high-valent iron-oxo species and a monomeric PhIO species) in thioanisole sulfoxidation to present different reaction mechanisms (the novel bond-cleavage coupled electron transfer mechanism or the direct oxygen-atom transfer mechanism) as a response to different substrate attack orientations. © 2017 American Chemical Society.
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