Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

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.

Original languageEnglish (US)
Article numbere202203906
JournalChemistry - A European Journal
Volume29
Issue number32
DOIs
StatePublished - Jun 7 2023

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis
  • Organic Chemistry

Keywords

  • cyanide
  • density functional calculations
  • nucleophilic substitution
  • phosphines
  • polysulfide reactivity
  • sulfur

Fingerprint

Dive into the research topics of 'Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**'. Together they form a unique fingerprint.

Cite this