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https://hdl.handle.net/10316/101237
Título: | S-H rotamerization via tunneling in a thiol form of thioacetamide | Autor: | Góbi, Sándor Nunes, Cláudio M Reva, Igor Tarczay, György Fausto, Rui |
Data: | 21-Ago-2019 | Editora: | Royal Society of Chemistry | Projeto: | info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT info:eu-repo/grantAgreement/FCT/UID/QUI/0313/2019 |
Título da revista, periódico, livro ou evento: | Physical Chemistry Chemical Physics | Volume: | 21 | Número: | 31 | Resumo: | Rotamerization of a hydroxyl (O-H) group by tunneling is well-known and has been extensively studied. On the other hand, similar tunneling processes for the thiol (S-H) group have not been reported yet. In this work, the imino-thiol forms of thioacetamide were studied in cryogenic matrices (Ar, Xe) after UV-irradiation of the common amino-thione form of the compound. Four different imino-thiol forms were generated, corresponding to the cis or trans thiol (C/T) conformers of the two imino isomers (syn and anti; s/a). Noteworthy, the syn-cis (sC) imino-thiol form was found to convert spontaneously to the syn-trans (sT) form (with a half-life of 80 min), in a process whose reaction rate is independent of the temperature (i.e., at 11 or 20 K). Such conformational transformation represents the first experimental observation of an S-H rotamerization occurring by tunneling. Computations based on the Wentzel-Kramers-Brillouin formalism predict a tunneling half-life for the S-H rotamerization of syn-imino sC to sT on the time scale of minutes, in agreement with the experimental observations. | URI: | https://hdl.handle.net/10316/101237 | DOI: | 10.1039/c9cp03417j | Direitos: | embargoedAccess |
Aparece nas coleções: | I&D CQC - Artigos em Revistas Internacionais |
Ficheiros deste registo:
Ficheiro | Descrição | Tamanho | Formato | |
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PCCP-2019-21-17063.pdf | 3.87 MB | Adobe PDF | Ver/Abrir |
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