Thione-thiol tautomerism of thiourea ligands on silica surface
Quantum chemical calculations of the IR spectra of the thione and thiol forms of N, N'-dimethylthiourea and silica surface fragment with composition (HO)3SiCH2NHC(S)NHCH3 (density functional theory method, B3LYP/6-31G (d, p)) make it possible to fix indicator absorption bands of the tautomers....
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Chuiko Institute of Surface Chemistry of NAS of Ukraine
2015-05-01
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| Series: | Хімія, фізика та технологія поверхні |
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| Online Access: | https://cpts.com.ua/index.php/cpts/article/view/329 |
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| author | O. V. Smirnova A. G. Grebenyuk G. I. Nazarchuk Yu. L. Zub |
| author_facet | O. V. Smirnova A. G. Grebenyuk G. I. Nazarchuk Yu. L. Zub |
| author_sort | O. V. Smirnova |
| collection | DOAJ |
| description | Quantum chemical calculations of the IR spectra of the thione and thiol forms of N, N'-dimethylthiourea and silica surface fragment with composition (HO)3SiCH2NHC(S)NHCH3 (density functional theory method, B3LYP/6-31G (d, p)) make it possible to fix indicator absorption bands of the tautomers. The presence of absorption bands at 1586 cm-1 (or 1607 cm-1 in the case of surface fragment) reveals the thione form whereas appearance of the intensive absorption bands at 1714 (1707)cm -1 indicates the occurrence of the thiol form. The results of quantum chemical calculations on the total energy of the transition complex in vacuum at T = 298 K and on the activation energy values of thione-thiol tautomeric transition between different conformations of the cluster models have shown a decrease in the activation barrier due to the grafting of thiourea groups on silica surface. The configurations of the transition complexes were also determined. |
| format | Article |
| id | doaj-art-4ef4db5c5f5044828b7b0bbd202dd73e |
| institution | Kabale University |
| issn | 2079-1704 2518-1238 |
| language | English |
| publishDate | 2015-05-01 |
| publisher | Chuiko Institute of Surface Chemistry of NAS of Ukraine |
| record_format | Article |
| series | Хімія, фізика та технологія поверхні |
| spelling | doaj-art-4ef4db5c5f5044828b7b0bbd202dd73e2025-08-20T03:31:10ZengChuiko Institute of Surface Chemistry of NAS of UkraineХімія, фізика та технологія поверхні2079-17042518-12382015-05-016210.15407/hftp06.02.224Thione-thiol tautomerism of thiourea ligands on silica surfaceO. V. Smirnova0A. G. Grebenyuk1G. I. Nazarchuk2Yu. L. Zub3Chuiko Institute of Surface Chemistry of National Academy of Sciences of UkraineChuiko Institute of Surface Chemistry of National Academy of Sciences of UkraineChuiko Institute of Surface Chemistry of National Academy of Sciences of UkraineChuiko Institute of Surface Chemistry of National Academy of Sciences of UkraineQuantum chemical calculations of the IR spectra of the thione and thiol forms of N, N'-dimethylthiourea and silica surface fragment with composition (HO)3SiCH2NHC(S)NHCH3 (density functional theory method, B3LYP/6-31G (d, p)) make it possible to fix indicator absorption bands of the tautomers. The presence of absorption bands at 1586 cm-1 (or 1607 cm-1 in the case of surface fragment) reveals the thione form whereas appearance of the intensive absorption bands at 1714 (1707)cm -1 indicates the occurrence of the thiol form. The results of quantum chemical calculations on the total energy of the transition complex in vacuum at T = 298 K and on the activation energy values of thione-thiol tautomeric transition between different conformations of the cluster models have shown a decrease in the activation barrier due to the grafting of thiourea groups on silica surface. The configurations of the transition complexes were also determined.https://cpts.com.ua/index.php/cpts/article/view/329mesoporous silicathione-thiol tautomerismIR spectroscopyquantum chemical calculationsdensity functional theory method |
| spellingShingle | O. V. Smirnova A. G. Grebenyuk G. I. Nazarchuk Yu. L. Zub Thione-thiol tautomerism of thiourea ligands on silica surface Хімія, фізика та технологія поверхні mesoporous silica thione-thiol tautomerism IR spectroscopy quantum chemical calculations density functional theory method |
| title | Thione-thiol tautomerism of thiourea ligands on silica surface |
| title_full | Thione-thiol tautomerism of thiourea ligands on silica surface |
| title_fullStr | Thione-thiol tautomerism of thiourea ligands on silica surface |
| title_full_unstemmed | Thione-thiol tautomerism of thiourea ligands on silica surface |
| title_short | Thione-thiol tautomerism of thiourea ligands on silica surface |
| title_sort | thione thiol tautomerism of thiourea ligands on silica surface |
| topic | mesoporous silica thione-thiol tautomerism IR spectroscopy quantum chemical calculations density functional theory method |
| url | https://cpts.com.ua/index.php/cpts/article/view/329 |
| work_keys_str_mv | AT ovsmirnova thionethioltautomerismofthiourealigandsonsilicasurface AT aggrebenyuk thionethioltautomerismofthiourealigandsonsilicasurface AT ginazarchuk thionethioltautomerismofthiourealigandsonsilicasurface AT yulzub thionethioltautomerismofthiourealigandsonsilicasurface |