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Matrix Isolation IR Spectroscopic Investigation of S-H···S-S H-Bond in H2S-Diethyl Disulfide Complex
Ankita Kothari1, Binod Kumar Oram1,2,3, Biman Bandyopadhyay1
1Department of Chemistry, Malaviya National Institute of Technology Jaipur, J L N Marg, Jaipur 302017, India.
The Journal of Physical Chemistry. A
|April 21, 2025
Summary
Hydrogen sulfide (H2S) forms multiple S-H···S-S hydrogen bonds with diethyl disulfide (DEDS). The S-S bond in DEDS is a superior hydrogen bond acceptor compared to sulfur in H2S.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Computational Chemistry
Background:
- Hydrogen bonding plays a crucial role in molecular interactions.
- Sulfur-centered hydrogen bonds are less explored compared to oxygen-centered ones.
- Diethyl disulfide (DEDS) contains a reactive S-S bond capable of participating in non-covalent interactions.
Purpose of the Study:
- To investigate the formation and characteristics of S-H···S-S hydrogen bonds between H2S and DEDS.
- To compare the hydrogen bonding capabilities of the S-S linkage in DEDS with other sulfur-containing molecules.
- To explore the influence of matrix environment (Argon vs. Nitrogen) on complex stability and formation.
Main Methods:
- Fourier Transform Infrared (FTIR) spectroscopy was employed to study the complexes in solid argon and nitrogen matrices.
- Computational methods were used to calculate binding energies and activation barriers for complex interconversion.
- Analysis of spectral shifts and band intensities provided insights into the hydrogen bond strength and number.
Main Results:
- 1:1 complexes of H2S with DEDS were successfully identified, forming one or two S-H···S-S hydrogen bonds.
- Five distinct H-bonded complexes were observed for the two lowest energy rotamers of DEDS.
- Binding energies ranged from 2.43 to 3.05 kcal mol⁻¹, with activation barriers from 0.08 to 2.65 kcal mol⁻¹.
- The S-S linkage in DEDS proved to be a more effective hydrogen bond acceptor than the sulfur atom in H2S.
- Complexes were more readily observed in N2 matrices compared to Ar matrices due to matrix effects.
Conclusions:
- The S-S bond in DEDS is an efficient acceptor for S-H hydrogen bonds.
- Dispersion interactions significantly contribute to the stabilization of these sulfur-centered hydrogen-bonded complexes.
- This study provides valuable data on the nature of sulfur-centered hydrogen bonds, expanding our understanding of non-covalent interactions.
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