3 years ago

Fast Heavy-Atom Tunneling in Trifluoroacetyl Nitrene

Hongmin Li, Guohai Deng, Xiaoqing Zeng, Ruijuan Feng, Didier Bégué, Manabu Abe, Kun Liu, Zhuang Wu, Jian Xu
Chemical reactions involving quantum mechanical tunneling (QMT) increasingly attract the attention of natural scientists. In contrast to the hydrogen-tunneling as frequently observed in chemistry and biology, tunneling solely by heavy atoms is rare. Herein, we report the clear-cut heavy-atom tunneling in trifluoroacetyl nitrene, CF3C(O)N. Specifically, the carbonyl nitrene CF3C(O)N in the triplet ground state was generated in cryogenic matrices by laser (193 or 266 nm) photolysis of CF3C(O)N3 and characterized by IR and EPR spectroscopy. In contrast to the theoretically predicted activation barriers (> 10 kcal mol-1), CF3C(O)N undergoes rapid rearrangement into CF3NCO with half-life times of less than 10 minutes and unprecedentedly large 14N/15N kinetic isotope effects (1.18-1.33) in solid Ar, Ne, and N2 matrices even at 2.8 K. The tunneling disappearance of CF3C(O)N becomes much slower in the chemically active toluene and in 2-methyltetrahydrofuran at 5 K.

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

DOI: 10.1002/anie.201710307

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.