Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**
Document Type
Article
Publication Date
6-7-2023
Abstract
The reactions of elemental sulfur (S8) and polysulfides with nucleophiles are relevant to organic synthesis, materials science and biochemistry, but the mechanisms by which they operate are still unknown due to the inherent thermodynamic and kinetic instability of polysulfide intermediates. Using Density Functional Theory (DFT) calculations at the ωB97X-D/aug-cc-pV(T+d)Z/SMD(MeCN) // ωB97X-D/aug-cc-pVDZ/SMD(MeCN) level of theory, we studied the mechanisms behind the reaction of elemental sulfur and polysulfides with cyanide and phosphines, which quantitatively generate the monosulfide products thiocyanate and phosphine sulfides, respectively. All plausible pathways including nucleophilic decomposition, unimolecular decomposition, scrambling reactions, and attack on thiosulfoxides, have been considered to provide the first comprehensive mechanistic picture for this class of reactions. Overall, intramolecular cyclization is identified as the most favorable decomposition pathway for long polysulfides. For short polysulfides, a mixture of unimolecular decomposition, nucleophilic attack, and scrambling pathways can be expected.
Identifier
85153771327 (Scopus)
Publication Title
Chemistry A European Journal
External Full Text Location
https://doi.org/10.1002/chem.202203906
e-ISSN
15213765
ISSN
09476539
PubMed ID
37010258
Issue
32
Volume
29
Grant
61891‐DNI4
Fund Ref
American Cancer Society
Recommended Citation
Sharma, Jyoti and Champagne, Pier Alexandre, "Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**" (2023). Faculty Publications. 1664.
https://digitalcommons.njit.edu/fac_pubs/1664