H2S Generation from CS2 Hydrolysis at a Dinuclear Zinc(II) Site
Ananya Saju1, Aditesh Mondal1, Taraknath Chattopadhyay1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM), Thiruvananthapuram 695551, India.
Inorganic Chemistry
|October 22, 2020
Summary
This study demonstrates a zinc(II)-aqua complex effectively hydrolyzes carbon disulfide (CS2) to produce hydrogen sulfide (H2S), a crucial step for therapeutic applications. The research highlights the role of zinc(II)-hydroxide sites in this catalytic process.
Area of Science:
- Inorganic Chemistry
- Bioinorganic Chemistry
- Catalysis
Background:
- Controlled generation of hydrogen sulfide (H2S) is vital for therapeutic applications.
- Phenolate-bridged dinuclear zinc(II) complexes serve as potential hydrolase models.
Purpose of the Study:
- To investigate the catalytic activity of a dinuclear zinc(II)-aqua complex in carbon disulfide (CS2) hydrolysis.
- To elucidate the mechanism of H2S generation from CS2 using zinc(II) complexes.
- To explore the role of coordination sites and active zinc(II) species in CS2 hydrolysis.
Main Methods:
- Synthesis and characterization of dinuclear zinc(II) complexes.
- Study of the reactivity of zinc(II) complexes with CS2 in the presence of triethylamine (Et3N).
- Mass spectrometric analysis of reaction intermediates and products.
Main Results:
- The dinuclear zinc(II)-aqua complex (1a) efficiently hydrolyzes CS2 to H2S.
- Penta-coordinated zinc(II) sites in other dinuclear complexes do not mediate CS2 hydrolysis.
- Tetranuclear zinc(II) complexes with [ZnII]-OH sites show reactivity towards CS2, indicating the nucleophilic role of the hydroxide.
- Mechanistic insights suggest the involvement of zinc(II)-thiocarbonate and carbonyl sulfide (COS) intermediates.
Conclusions:
- Dinuclear zinc(II)-aqua complexes can act as effective hydrolase models for H2S generation from CS2.
- The presence of accessible coordination sites for water and active [ZnII]-OH moieties are crucial for CS2 hydrolysis.
- This work provides a foundation for developing novel catalysts for controlled H2S production.
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