Electrochemical reduction, radical anions, and dehalogenation of fluorinated/chlorinated 2,1,3-benzothia/selenadiazoles

Electrochemical reduction, radical anions, and dehalogenation of fluorinated/chlorinated 2,1,3-benzothia/selenadiazoles Full article

Journal

ARKIVOC
ISSN: 1551-7004 , E-ISSN: 1551-7012

Output data

Year: 2017, Pages: 166-180 Pages count : 15 DOI: 10.24820/ark.5550190.p010.116

Tags

2,1,3-Benzothiadiazoles; 2,1,3-benzoselenadiazoles; chlorinated; cyclic voltammetry; dehalogenation; DFT; EPR; fluorinated; radical anions

Authors

Shundrin Leonid A. ^1,2 , Irtegova Irina G. ¹ , Avrorov Pavel A. ¹ , Mikhailovskaya Tatiana F. ¹ , Makarov Arkady G. ¹ , Makarov Alexander Yu. ¹ , Zibarev Andrey V. ^1,3

Affiliations

1	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Nat Sci, Novosibirsk 630090, Russia
3	(Данные Web of science) Tomsk State Univ, Natl Res Univ, Dept Chem, Tomsk 634050, Russia

At the first stage of electrochemical reduction in DMF, fluorinated/chlorinated 2,1,3-benzothia/selenadiazoles formed long-lived radical anions characterized by EPR and DFT. Gas-phase electron affinities (EA(1)) from DFT correlated well with the first-peak potentials separately for S and Se derivatives, and the latter were found to be better electron acceptors than the former in contrast to the atomic EA(1) and Allen electronegativity. At the second stage, chalcogen- and halogen-dependent dehalogenation proceeded: non-hydrodefluorination of selenadiazoles through their n-electron activation (n >= 2), and hydrodechlorination of thia/selenadiazoles through H+ addition to their dianions. These differ from dehalogenation of related (aza) aromatics (e.g. benzenes, naphthalenes, quinoxalines).

Shundrin L.A. , Irtegova I.G. , Avrorov P.A. , Mikhailovskaya T.F. , Makarov A.G. , Makarov A.Y. , Zibarev A.V.
Electrochemical reduction, radical anions, and dehalogenation of fluorinated/chlorinated 2,1,3-benzothia/selenadiazoles
ARKIVOC. 2017. P.166-180. DOI: 10.24820/ark.5550190.p010.116 WOS Scopus РИНЦ

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