Thione-thiol tautomerism of thiourea ligands on silica surface

  • O. V. Smirnova Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
  • A. G. Grebenyuk Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
  • G. I. Nazarchuk Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
  • Yu. L. Zub Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
DOI: https://doi.org/10.15407/hftp06.02.224
Keywords: mesoporous silica, thione-thiol tautomerism, IR spectroscopy, quantum chemical calculations, density functional theory method

Abstract

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.

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How to Cite
SMIRNOVA, O. V.; GREBENYUK, A. G.; NAZARCHUK, G. I.; ZUB, Y. L. Thione-thiol tautomerism of thiourea ligands on silica surface. Chemistry, Physics and Technology of Surface, v. 6, n. 2, p. 224-233, 11.
Issue
Vol. 6 No. 2 (2015): Chemistry, Physics and Technology of Surface / Himia, Fizika ta Tehnologia Poverhni
Section
Articles
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