TY - JOUR

T1 - Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange

AU - Konstantinova, Lidia S.

AU - Baranovsky, Ilia V.

AU - Pritchina, Elena A.

AU - Mikhailov, Maksim S.

AU - Bagryanskaya, Irina Yu

AU - Semenov, Nikolay A.

AU - Irtegova, Irina G.

AU - Salnikov, Georgy E.

AU - Lyssenko, Konstantin A.

AU - Gritsan, Nina P.

AU - Zibarev, Andrey V.

AU - Rakitin, Oleg A.

N1 - Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/12/1

Y1 - 2017/12/1

N2 - 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.

AB - 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.

KW - density functional calculations

KW - dithiazoles

KW - synthetic methods

KW - thiaselenazoles

KW - X-ray diffraction

KW - ANO BASIS-SETS

KW - ELECTROCHEMICAL PROPERTIES

KW - STRUCTURAL-CHARACTERIZATION

KW - 4,5-DICHLORO-1,2,3-DITHIAZOLIUM CHLORIDE

KW - 1,2,3-BENZODITHIAZOLYL RADICALS

KW - SET MODEL CHEMISTRY

KW - HETEROCYCLIC RADICAL-ANION

KW - MOLECULAR WAVE-FUNCTIONS

KW - CHARGE-TRANSFER CHEMISTRY

KW - 1,2,5-CHALCOGENADIAZOLE DERIVATIVES

UR - http://www.scopus.com/inward/record.url?scp=85034055502&partnerID=8YFLogxK

U2 - 10.1002/chem.201703182

DO - 10.1002/chem.201703182

M3 - Article

C2 - 28885741

AN - SCOPUS:85034055502

VL - 23

SP - 17037

EP - 17047

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 67

ER -