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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
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Direct hydrogen selenide (H2Se) release from activatable selenocarbamates.
Turner D Newton1, Keyan Li1, Jyoti Sharma2
1Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon Eugene Oregon 97403-1253 USA pluth@uoregon.edu.
Chemical Science
|July 14, 2023
Summary
Researchers found that selenocarbamates directly release hydrogen selenide (H₂Se), unlike related sulfur compounds. This discovery offers new methods for delivering H₂Se for biological research.
Area of Science:
- Bioinorganic Chemistry
- Chemical Biology
- Organoselenium Chemistry
Background:
- Hydrogen selenide (H₂Se) is a crucial molecule in biology, acting as a bioregulator and precursor for organoselenium compounds.
- Existing methods for delivering hydrogen sulfide (H₂S) involve thiocarbamates releasing carbonyl sulfide (COS), which is then converted to H₂S.
- Understanding H₂Se delivery mechanisms is vital for advancing biological research.
Purpose of the Study:
- To investigate the chemical mechanisms by which selenocarbamates release H₂Se.
- To determine if selenocarbamates follow a similar pathway to thiocarbamates, involving carbonyl selenide (COSe) intermediates.
- To explore novel small-molecule-based approaches for H₂Se delivery.
Main Methods:
- Synthesis and study of selenocarbamates.
- Utilizing both light- and hydrolysis-activated systems for H₂Se release.
- Employing computational investigations to analyze reaction pathways and energy barriers.
Main Results:
- Selenocarbamates directly release H₂Se, accompanied by isocyanate formation.
- The release mechanism does not involve a carbonyl selenide (COSe) intermediate.
- Computational studies revealed a significant energy difference favoring direct H₂Se release over COSe formation.
Conclusions:
- This study reveals a novel direct H₂Se release mechanism from selenocarbamates.
- The findings highlight fundamental differences in reactivity between sulfur and selenium analogs.
- New avenues for designing small molecules for H₂Se delivery in biological systems are established.
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