Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation
Douglas W. Stephan, Levy L. Cao, Yue Shao, Liu Leo Liu
Single electron transfer (SET) reactions are effected by the combination of a Lewis acid (e.g., E(C6F5)3 E = B or Al) with a small molecule substrate and decamethylferrocene (Cp*2Fe). Initially, the corresponding reactions of (PhS)2 and (PhTe)2 were shown to give the species [Cp*2Fe][PhSB(C6F5)3] 1 and [Cp*2Fe][(μ-PhS)(Al(C6F5)3)2] 2 and [Cp*2Fe][(μ-PhTe)(Al(C6F5)3)2] 3, respectively. Analogous reactions with di-tert-butyl peroxide yielded [Cp*2Fe][(μ-HO)(B(C6F5)3)2] 4 with isobutene while with benzoyl peroxide afforded [Cp*2Fe][PhC(O)OE(C6F5)3] (E = B 5, Al 6). Evidence for a radical pathway was provided by the reaction of Ph3SnH and p-quinone afforded [Cp*2Fe][HB(C6F5)3] 7 and [Cp*2Fe]2[(μ-O2C6H4)(E(C6F5)3)2] (E = B 8, Al 9). In addition, the reaction of TEMPO with Lewis acid and Cp*2Fe afforded [Cp*2Fe][(C5H6Me4NOE(C6F5)3] (E = B 10, Al 11). Finally, reactions with O2, Se, Te and S8 gave [Cp*2Fe]2[((C6F5)2Al(μ-O)Al(C6F5)3)2]2 12, [Cp*2Fe]2[((C6F5)2Al(μ-Se)Al(C6F5)3)2]2 13, [Cp*2Fe][(μ-Te)2(Al(C6F5)2)3] 14 and [Cp*2Fe]2[(μ-S7)B(C6F5)3)2] 15, respectively. The mechanisms of these SET reactions are discussed, and the ramifications are considered.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05120

DOI: 10.1021/jacs.7b05120

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.