5 years ago

From Si(II) to Si(IV) and Back: Reversible Intramolecular Carbon–Carbon Bond Activation by an Acyclic Iminosilylene

From Si(II) to Si(IV) and Back: Reversible Intramolecular Carbon–Carbon Bond Activation by an Acyclic Iminosilylene
Christian Jandl, Fabian A. D. Herz, Bernhard Rieger, Shigeyoshi Inoue, Debotra Sarkar, Amelie Porzelt, Daniel Wendel
Reversibility is fundamental for transition metal catalysis, but equally for main group chemistry and especially low-valent silicon compounds, the interplay between oxidative addition and reductive elimination is key for a potential catalytic cycle. Herein, we report a highly reactive acyclic iminosilylsilylene 1, which readily performs an intramolecular insertion into a C═C bond of its aromatic ligand framework to give silacycloheptatriene (silepin) 2. UV–vis studies of this Si(IV) compound indicated a facile transformation back to Si(II) at elevated temperatures, further supported by density functional theory calculations and experimentally demonstrated by isolation of a silylene–borane adduct 3 following addition of B(C6F5)3. This tendency to undergo reductive elimination was exploited in the investigation of silepin 2 as a synthetic equivalent of silylene in the activation of small molecules. In fact, the first monomeric, four-coordinate silicon carbonate complex 4 was isolated and fully characterized in the reaction with carbon dioxide under mild conditions. Additionally, the exposure of 2 to ethylene or molecular hydrogen gave silirane 5 and Si(IV) dihydride 6, respectively.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05136

DOI: 10.1021/jacs.7b05136

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.