Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 67, Pages 17037-17047Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201703182
Keywords
density functional calculations; dithiazoles; synthetic methods; thiaselenazoles; X-ray diffraction
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Funding
- Russian Science Foundation [15-13-10022]
- Russian Federal Ministry for Education and Science within the 5-100 Excellence Program
- Russian Federal Agency of Scientific Organizations [0304-2014-0003]
- Russian Science Foundation [15-13-10022] Funding Source: Russian Science Foundation
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A new approach to the synthesis of fused 1,2,3-thiaselenazolesrare five-membered heterocycles that contain two different chalcogensfrom 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 (SeNMR)-Se-77 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 * or sigma* SOMOs, respectively.
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