"Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with C" by Jyoti Sharma and Pier Alexandre Champagne
 

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

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