Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange

Lidia S. Konstantinova, Ilia V. Baranovsky, Elena A. Pritchina, Maksim S. Mikhailov, Irina Yu Bagryanskaya, Nikolay A. Semenov, Irina G. Irtegova, Georgy E. Salnikov, Konstantin A. Lyssenko, Nina P. Gritsan, Andrey V. Zibarev, Oleg A. Rakitin

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

A new approach to the synthesis of fused 1,2,3-thiaselenazoles—rare five-membered heterocycles that contain two different chalcogens—from the corresponding 1,2,3-dithiazoles and SeO2 was accomplished by selective exchange of S and Se atoms. The fused carbo- and heterocyclic units were indene, naphthalenone, cyclohexadienone, cyclopentadiene, benzoannulene, and benzoxazine. The molecular structures of two of the thiaselenadiazole products and one of the dithiazole precursors were confirmed by single-crystal X-ray diffraction. The reaction is highly solvent selective; it only takes place in solvents that contain a C=O group (e.g., DMF or tetramethylurea). According to DFT calculations, the reaction is thermodynamically favorable. Based on the DFT calculations and 77Se NMR spectroscopy, two tentative mechanisms that feature isomeric transition states and intermediates are suggested for the reaction via ring-opening addition of SeO2 to the S−X dithiazole bond (X=N or S). The DFT-calculated first adiabatic electron affinities of the compounds were chalcogen independent and positive in all cases, which assumes formation of thermodynamically stable radical anions (RAs). These calculated RAs featured either normal or abnormal elongation of the S1−X2 (X=S or Se) bond relative to their neutral precursors and possessed π* or σ* SOMOs, respectively.

Original languageEnglish
Pages (from-to)17037-17047
Number of pages11
JournalChemistry - A European Journal
Volume23
Issue number67
DOIs
Publication statusPublished - 1 Dec 2017

Keywords

  • density functional calculations
  • dithiazoles
  • synthetic methods
  • thiaselenazoles
  • X-ray diffraction
  • ANO BASIS-SETS
  • ELECTROCHEMICAL PROPERTIES
  • STRUCTURAL-CHARACTERIZATION
  • 4,5-DICHLORO-1,2,3-DITHIAZOLIUM CHLORIDE
  • 1,2,3-BENZODITHIAZOLYL RADICALS
  • SET MODEL CHEMISTRY
  • HETEROCYCLIC RADICAL-ANION
  • MOLECULAR WAVE-FUNCTIONS
  • CHARGE-TRANSFER CHEMISTRY
  • 1,2,5-CHALCOGENADIAZOLE DERIVATIVES

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