Please use this identifier to cite or link to this item: https://hdl.handle.net/10316/101242
Title: Switching on H-Tunneling through Conformational Control
Authors: Roque, José P. L. 
Nunes, Cláudio M. 
Viegas, Luís P. 
Pereira, Nelson A. M. 
Pinho e Melo, Teresa M. V. D. 
Schreiner, Peter R.
Fausto, Rui 
Issue Date: 2021
Publisher: American Chemical Society
Project: info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT 
PTDC/QUI-QFI/1880/2020 
UIDB/QUI/0313/2020 
UIDP/QUI/0313/2020 
Serial title, monograph or event: Journal of the American Chemical Society
Volume: 143
Issue: 22
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 N2 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 2ν(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.
URI: https://hdl.handle.net/10316/101242
ISSN: 0002-7863
1520-5126
DOI: 10.1021/jacs.1c04329
Rights: embargoedAccess
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais

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