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https://hdl.handle.net/10316/17880
Título: | Double-Proton-Transfer Processes in Dithiooxamide: UV-Induced Dithione → Dithiol Reaction and Ground-State Dithiol → Dithione Tunneling | Autor: | Lapinski, Leszek Rostkowska, Hanna Khvorostov, Artem Yaman, Müjgan Fausto, Rui Nowak, Maciej J. |
Data: | Mai-2004 | Editora: | American Chemical Society | Título da revista, periódico, livro ou evento: | J. Phys. Chem. A | Volume: | 108 | Resumo: | Dithiooxamide [rubeanic acid, NH2C(S)C(S)NH2)] monomers were studied by FTIR spectroscopy combined with the low-temperature matrix-isolation technique. The most stable dithione−diamino tautomer of the compound was exclusively observed in argon matrixes immediately after deposition. Upon UV (λ > 345 nm) irradiation the dithione−diamino form transformed, by a double-proton transfer, into the dithiol−diimino tautomer. Theoretically supported analysis of the infrared spectrum emerging upon UV irradiation allowed identification of one of the conformers of the dithiol−diimino tautomer as the dominating photoproduct. Smaller quantities of other conformers of the dithiol−diimino tautomer were also found to be photogenerated. For the UV-irradiated matrix kept subsequently at 10 K and in darkness, a dithiol−diimino → dithione−diamino tautomerization leading to partial recovery of the initial form of the compound was observed. The only possible mechanism of this ground-state transformation at cryogenic temperature is synchronous double-proton tunneling. The experimentally obtained time constant of this process was 18 h. | URI: | https://hdl.handle.net/10316/17880 | DOI: | 10.1021/jp049263w | Direitos: | openAccess |
Aparece nas coleções: | FCTUC Química - Artigos em Revistas Internacionais |
Ficheiros deste registo:
Ficheiro | Descrição | Tamanho | Formato | |
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J.Physical Chemistry A, 108 (2004) 5551.pdf | 184.61 kB | Adobe PDF | Ver/Abrir |
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