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Nitroxyl disulfides, novel intermediates in transnitrosation reactions
K N Houk1, Bruce N Hietbrink, Michael D Bartberger
1Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095-1569, USA. houk@chem.ucla.edu
Journal of the American Chemical Society
|June 5, 2003
Summary
Researchers computationally explored a novel anionic species, a key intermediate in transnitrosation reactions. This nitroxyl disulfide intermediate was characterized by its unique structure and reactivity, confirmed by mass spectrometry.
Area of Science:
- Computational chemistry
- Reaction mechanisms
- Organic chemistry
Background:
- Transnitrosation reactions are crucial in various chemical processes.
- Understanding reaction intermediates is key to controlling reaction outcomes.
- Previous studies have not fully characterized the anionic intermediate in transnitrosation.
Purpose of the Study:
- To computationally investigate a novel anionic RSN(O)SR species, the intermediate in transnitrosation reactions.
- To compare the reactivity and structure of this intermediate with those in related reactions.
- To provide experimental evidence supporting the formation of this intermediate.
Main Methods:
- Density functional theory (DFT) calculations using B3LYP and CBS-QB3 methods.
- Computation of reaction pathways for related species (e.g., MeS(-) + MeSNO).
- Gas-phase mass spectrometry experiments.
Main Results:
- The novel anionic species was identified as a nitroxyl coordinated to a distorted disulfide.
- Significant differences were observed in the intermediates compared to nucleophilic acyl substitution.
- Mass spectrometry provided experimental evidence consistent with the formation of the nitroxyl disulfide intermediate.
- Proton affinity and redox potentials of the intermediate were calculated.
Conclusions:
- The study elucidates the structure and properties of a novel anionic intermediate in transnitrosation.
- The findings offer insights into the mechanism of transnitrosation reactions.
- Experimental evidence supports the computational predictions, validating the existence of the nitroxyl disulfide intermediate.
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