z-logo
Premium
Fast Heavy‐Atom Tunneling in Trifluoroacetyl Nitrene
Author(s) -
Wu Zhuang,
Feng Ruijuan,
Li Hongmin,
Xu Jian,
Deng Guohai,
Abe Manabu,
Bégué Didier,
Liu Kun,
Zeng Xiaoqing
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201710307
Subject(s) - nitrene , chemistry , quantum tunnelling , photodissociation , kinetic isotope effect , photochemistry , hydrogen atom , atom (system on chip) , spectroscopy , hydrogen , atomic physics , materials science , organic chemistry , physics , deuterium , catalysis , quantum mechanics , computer science , embedded system , alkyl , optoelectronics
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, CF 3 C(O)N. The carbonyl nitrene CF 3 C(O)N in the triplet ground state was generated in cryogenic matrices by laser (193 or 266 nm) photolysis of CF 3 C(O)N 3 and characterized by IR and EPR spectroscopy. In contrast to the theoretically predicted activation barriers (>10 kcal mol −1 ), CF 3 C(O)N undergoes rapid rearrangement into CF 3 NCO with half‐life times of less than 10 min and unprecedentedly large 14 N/ 15 N kinetic isotope effects (1.18–1.33) in solid Ar, Ne, and N 2 matrices even at 2.8 K. The tunneling disappearance of CF 3 C(O)N becomes much slower in the chemically active toluene and in 2‐methyltetrahydrofuran at 5 K.

This content is not available in your region!

Continue researching here.

Having issues? You can contact us here