Crossover point between dialkoxy disulfides (ROSSOR) and thionosulfites ((RO)(2)S=S): Prediction, synthesis, and structure

E Zysman-Colman, N Nevins, N Eghbali, JP Snyder*, DN Harpp

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

21 Citations (Scopus)

Abstract

Isomeric preference between cyclic dialkoxy disulfides and thionosulfites is governed by the ring size of the heterocycle. Rings smaller than seven atoms prefer the thionosulfite connectivity, whereas larger rings or acyclic analogues favor the unbranched dialkoxy disulfide structure. Density functional calculations were employed to predict the crossover point at which both constitutional isomers are of comparable stability. Follow-up synthesis provides the previously unknown eight-membered ring dialkoxy disulficle 14 and seven-membered ring thionosulfite 15 from the same reaction. X-ray crystallography for all but one of the reaction products and complementary NMR analysis furnishes insights into both solid-state and solution conformations. A long-standing issue regarding the concerted vs catalyzed isomerization pathway between XSSX and X2S = S has been addressed for X = RO and shown to be acid dependent.

Original languageEnglish
Pages (from-to)291-304
Number of pages14
JournalJournal of the American Chemical Society
Volume128
Issue number1
DOIs
Publication statusPublished - 11 Jan 2006

Keywords

  • BEWEGLICHKEIT FLEXIBLER RINGSYSTEME
  • INFRARED SPECTROSCOPIC EVIDENCE
  • NUCLEAR MAGNETIC-RESONANCE
  • MOLECULAR-ORBITAL METHODS
  • UNTERSUCHUNGEN MIT HILFE
  • BRANCH-BONDED SULFUR
  • GAUSSIAN-TYPE BASIS
  • ELECTRON-DIFFRACTION
  • PYRAMIDAL INVERSION
  • MICROWAVE-SPECTRUM

Fingerprint

Dive into the research topics of 'Crossover point between dialkoxy disulfides (ROSSOR) and thionosulfites ((RO)(2)S=S): Prediction, synthesis, and structure'. Together they form a unique fingerprint.

Cite this