3 years ago

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

Mutable Properties of Nonheme Iron(III)–Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism
Kyung-Bin Cho, Yong Wang, Wonwoo Nam, Xiao-Xi Li, Yiran Kang, Wei Sun, Chungu Xia
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b03310

DOI: 10.1021/jacs.7b03310

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.