Journal article

Publication year: 2021

Pages: 8266-8271

Journal: Journal of the American Chemical Society

Volume number: 143

Issue number: 22

ISSN: 0002-7863

Open access status: Green

DOI Link: https://doi.org/10.1021/jacs.1c04329

Publisher: American Chemical Society

Abstract: 
H-tunneling is a ubiquitous phenomenon, relevant to fields from biochemistry to materials science, but harnessing it for mastering the manipulation of chemical structures still remains nearly illusory. Here, we demonstrate how to switch on H-tunneling by conformational control using external radiation. This is outlined with a triplet 2-hydroxyphenylnitrene generated in an N-2 matrix at 10 K by UV-irradiation of an azide precursor. The anti-orientation of the nitrene's OH moiety was converted to syn by selective vibrational excitation at the 2v(OH) frequency, thereby moving the H atom closer to the vicinal nitrene center. This triggers spontaneous H-tunneling to a singlet 6-imino-2,4-cyclohexadienone. Computations reveal that such fast H-tunneling occurs through crossing the triplet-to-singlet potential energy surfaces. Our experimental realization provides an exciting novel strategy to attain control over tunneling, opening new avenues for directing chemical transformations.

Harvard Citation style: Roque, J., Nunes, C., Viegas, L., Pereira, N., Melo, T., Schreiner, P., et al. (2021) Switching on H-Tunneling through Conformational Control, Journal of the American Chemical Society, 143(22), pp. 8266-8271. https://doi.org/10.1021/jacs.1c04329

APA Citation style: Roque, J., Nunes, C., Viegas, L., Pereira, N., Melo, T., Schreiner, P., & Fausto, R. (2021). Switching on H-Tunneling through Conformational Control. Journal of the American Chemical Society. 143(22), 8266-8271. https://doi.org/10.1021/jacs.1c04329