Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism

Yiran Kang, Xiao Xi Li, Kyung Bin Cho, Wei Sun, Chungu Xia, Wonwoo Nam, Yong Wang

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)7444-7447
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number22
DOIs
StatePublished - 7 Jun 2017

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