曾小庆教授与广岛大学大学院理学研究科Manabu Abe教授合作在Angew. Chem. Int. Ed. 上发表研究论文

Fast Heavy-Atom Tunneling in Trifluoroacetyl Nitrene

Zhuang Wu^a, Ruijuan Feng^a, Hongmin Li^a, Jian Xu^a, Guohai Deng^a, Manabu Abe^*b, Didier B gu^c, Kun Liu^d, and Xiaoqing Zeng^*a（曾小庆）

^aCollege of Chemistry, Chemical Engineering and Materials Science,Soochow University,Suzhou 215123 (China)

^bDepartment of Chemistry, Graduate School of Science Hiroshima University,1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)

^cInstitut des Sciences Analytiques et de Physico-Chimie pour l’Environnement et les Mat_riaux, UMR5254, CNRS/ UNIV PAU &

Pays Adour, Pau 64000 (France)

^dCollege of Chemistry, Tianjin Normal University ,Tianjin 300387 (China)

Angew. Chem. Int. Ed. 2017, 56, 1 -- 6

Chemical reactions involving quantum mechanical tunneling (QMT) increasingly attract the attention of scientists. In contrast to the hydrogen-tunneling as frequently observed in chemistry and biology, tunneling solely by heavy atoms is rare. Herein, we report heavy-atom tunneling in trifluoroacetyl nitrene, CF₃C(O)N. 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 min 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.

链接：http://onlinelibrary.wiley.com/doi/10.1002/anie.201710307/abstract;jsessionid=CD32C5813A2E38BB94ED2FBD40BC4CDE.f04t01