Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
5 years ago

Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent-Silyliumylidene Cation

Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent-Silyliumylidene Cation
Emma Richards, Indu Purushothaman, Yongxin Li, Pattiyil Parameswaran, Yan Li, Yuk-Chi Chan, Susmita De, Cheuk-Wai So, Bi-Xiang Leong
The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6-iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− (1), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− (2) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1-F-2-IMe-C6H4]+I− (3). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1. Compounds 1–3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography. Unusual intermediates: The reaction of a cyclic (alkyl)(amino) carbene with H2SiI2 afforded a separated ion pair containing a cationic cAAC–silicon(I) radical complex (see scheme, left). On the other hand, treatment of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 with a different NHC led to an NHC–parent-silyliumylidene cation (right).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702760

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.