Utilize este identificador para referenciar este registo:
https://hdl.handle.net/10316/101242
Título: | Switching on H-Tunneling through Conformational Control | Autor: | 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 |
Data: | 2021 | Editora: | American Chemical Society | Projeto: | info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT PTDC/QUI-QFI/1880/2020 UIDB/QUI/0313/2020 UIDP/QUI/0313/2020 |
Título da revista, periódico, livro ou evento: | Journal of the American Chemical Society | Volume: | 143 | Número: | 22 | Resumo: | 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 | Direitos: | embargoedAccess |
Aparece nas coleções: | I&D CQC - Artigos em Revistas Internacionais |
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Ficheiro | Descrição | Tamanho | Formato | |
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JACS-2021-143-8266.pdf | 1.37 MB | Adobe PDF | Ver/Abrir |
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