Startseite Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations
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Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations

  • Muhammad H. Esmaiel , Hany A. Basuony , Mohamed K. Al-Nawasany , Musab M. Shulkamy , Ibrahim A. Shaaban , Ahmed M. Abuelela , Wajdi M. Zoghaib und Tarek A. Mohamed EMAIL logo
Veröffentlicht/Copyright: 22. Juni 2019
Zeitschrift für Physikalische Chemie
Aus der Zeitschrift Zeitschrift für Physikalische Chemie Band 234 Heft 3

Abstract

Raman (3700–100 cm−1) and infrared (4000–400 cm−1) spectra of 2,5-Dimercapto-1,3,4-thiadiazol (DMTD) were recorded in the solid phase. Six structures (1–6) were initially proposed for DMTD as a result of thiol-thione tautomerism and internal rotation(s) of thiol group(s) around the C–S bond. Quantum chemical calculations were carried out for an isolated molecule (1–6) using density functional theory (B3LYP) and ab initio MP2(full) methods utilizing 6-31G(d) and 6-311++G(d,p) basis sets which favor thiol-thione tautomerism (structure 4). Relaxed potential energy surface scans of structure 4 revealed an additional conformer (the thiol group is out-of-plane, structure 7) using the aforementioned methods at 6-311++G(d,p) basis set. For additional verification, plane-wave solid state calculations were carried out at PW91 and PBEsol came out in favor of conformer 7. This is in agreement with the computed/observed SH in-plane bending of S-7 (959/941 cm−1) rather than the one estimated at (880 cm−1) for S-4. Moreover, the observed split IR/Raman bands were found consistent with solid state calculated frequencies of S-7 assuming two molecules per unit cell bonded via H-bonding intermolecular interactions. Aided by vibrational frequency calculations, normal coordinate analysis, force constants and potential energy distributions (PEDs), a complete vibrational assignment for the observed IR and Raman bands is proposed herein. Furthermore, we have estimated the frontier molecular orbitals and atomic charges to account for the corrosion inhibition efficiency of DMTD along with its binding sites to the metal surface. Our results are discussed herein and compared to similar molecules whenever appropriate.

Keywords: 2,5-Dimercapto-1,3,4-thiadiazol (DMTD); tautomerism; Raman and infrared spectra; vibrational assignment and MP2 = full/DFT calculations

Acknowledgement

TAM sincerely thanks Professor James R. Durig, Chemistry Department, College of Arts and Sciences, University of Missouri, Kansas City, MO 64110, USA, for giving him the opportunity to use G- and F-matrix programs to calculate FCs in internal coordinates and PEDs.

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Supplementary Material

The online version of this article offers supplementary material (DOI: https://doi.org/10.1515/zpch-2018-1346).

Received: 2018-11-25
Accepted: 2019-05-20
Published Online: 2019-06-22
Published in Print: 2020-03-26

©2020 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. The Effect of Crystalline Microstructure of PVDF Binder on Mechanical and Electrochemical Performance of Lithium-Ion Batteries Cathode
  3. Mechanistic Study on Surface Tension of Binary and Ternary Mixtures Containing Choline Chloride, Ethylene Glycol and Water (Components of Aqueous Solutions of a Deep Eutectic Solvent, Ethaline)
  4. Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations
  5. The Thermodynamic and pH Metric Binding Studies of Cu+2 Ions with Egg Protein by Spectrometric and Diffusion Current Techniques
  6. Adsorption of 2,4-Dichlorophenoxyacetic Acid from Aqueous Solution Using Carbonized Chest Nut as Low Cost Adsorbent: Kinetic and Thermodynamic
  7. The Kinetics and Equilibrium Thermodynamics Study on the Removal of Direct Blue and Titan Yellow Dyes from Aqueous Media by Modified Rice Husk Char
  8. Investigation of Dielectric Properties, Electric Modulus and Conductivity of the Au/Zn-Doped PVA/n-4H-SiC (MPS) Structure Using Impedance Spectroscopy Method
  9. Finding Solvent for Polyamide 11 Using a Computer Software
  10. Phytochemical Synthesis of Silver Nanoparticles Using Anthemis Nobilis Extract and Its Antibacterial Activity
https://doi.org/10.1515/zpch-2018-1346
Schlagwörter für diesen Artikel
2,5-Dimercapto-1,3,4-thiadiazol (DMTD); tautomerism; Raman and infrared spectra; vibrational assignment and MP2 = full/DFT calculations

Artikel in diesem Heft

  1. Frontmatter
  2. The Effect of Crystalline Microstructure of PVDF Binder on Mechanical and Electrochemical Performance of Lithium-Ion Batteries Cathode
  3. Mechanistic Study on Surface Tension of Binary and Ternary Mixtures Containing Choline Chloride, Ethylene Glycol and Water (Components of Aqueous Solutions of a Deep Eutectic Solvent, Ethaline)
  4. Thiadiazole-2-Thiol-5-Thione and 2,5-Dimercapto-1,3,4-Thiadiazol Tautomerism, Conformational Stability, Vibrational Assignments, Inhibitor Efficiency and Quantum Chemical Calculations
  5. The Thermodynamic and pH Metric Binding Studies of Cu+2 Ions with Egg Protein by Spectrometric and Diffusion Current Techniques
  6. Adsorption of 2,4-Dichlorophenoxyacetic Acid from Aqueous Solution Using Carbonized Chest Nut as Low Cost Adsorbent: Kinetic and Thermodynamic
  7. The Kinetics and Equilibrium Thermodynamics Study on the Removal of Direct Blue and Titan Yellow Dyes from Aqueous Media by Modified Rice Husk Char
  8. Investigation of Dielectric Properties, Electric Modulus and Conductivity of the Au/Zn-Doped PVA/n-4H-SiC (MPS) Structure Using Impedance Spectroscopy Method
  9. Finding Solvent for Polyamide 11 Using a Computer Software
  10. Phytochemical Synthesis of Silver Nanoparticles Using Anthemis Nobilis Extract and Its Antibacterial Activity
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