TY - JOUR

T1 - Molecular ions of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1′-dioxides

AU - Shundrin, L. A.

AU - Irtegova, I. G.

AU - Rogachev, A. D.

AU - Reznikov, V. A.

N1 - Copyright: Copyright 2008 Elsevier B.V., All rights reserved.

PY - 2005/5

Y1 - 2005/5

N2 - The electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4- oxopyrrolinylidene) 1,1′-dioxides (R = CF3, Me, Ph, Bu t), which are cyclic dinitrons with conjugated C=C bond, in acetonitrile is an EE process producing stable radical anions and dianions, whereas the electrochemical oxidation is an EEC (R = Me, Ph) or EE process (R = But) with formation of radical cations (except for the case of R = CF3) and dications (R = But) stable under standard conditions. Radical cations of the dioxides with R = Me, Ph, and But and radical anions of the whole series of the compounds studied, including R = CF3, were characterized by ESR spectroscopy combined with electrochemical measurements and quantum-chemical calculations. The electrochemical behavior of the But-substituted dinitron is unique: the EE processes in the region of negative and positive potentials with formation of the dianion, radical anion, radical cation, and dication stable at T = 298 K were observed for the first time within one cycle of potential sweep in the CV curve measured in MeCN.

AB - The electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4- oxopyrrolinylidene) 1,1′-dioxides (R = CF3, Me, Ph, Bu t), which are cyclic dinitrons with conjugated C=C bond, in acetonitrile is an EE process producing stable radical anions and dianions, whereas the electrochemical oxidation is an EEC (R = Me, Ph) or EE process (R = But) with formation of radical cations (except for the case of R = CF3) and dications (R = But) stable under standard conditions. Radical cations of the dioxides with R = Me, Ph, and But and radical anions of the whole series of the compounds studied, including R = CF3, were characterized by ESR spectroscopy combined with electrochemical measurements and quantum-chemical calculations. The electrochemical behavior of the But-substituted dinitron is unique: the EE processes in the region of negative and positive potentials with formation of the dianion, radical anion, radical cation, and dication stable at T = 298 K were observed for the first time within one cycle of potential sweep in the CV curve measured in MeCN.

KW - 3,3′-bi(2-r-5,5-dimethyl-4-oxopyrrolinylidene) 1,1′-dioxides

KW - Cyclic nitrons

KW - Cyclic voltammetry

KW - Dianions

KW - Dications

KW - Electrooxidation

KW - Electroreduction

KW - ESR spectroscopy

KW - Radical anions

KW - Radical cations

UR - http://www.scopus.com/inward/record.url?scp=28444442722&partnerID=8YFLogxK

U2 - 10.1007/s11172-005-0377-2

DO - 10.1007/s11172-005-0377-2

M3 - Article

AN - SCOPUS:28444442722

VL - 54

SP - 1178

EP - 1184

JO - Russian Chemical Bulletin

JF - Russian Chemical Bulletin

SN - 1066-5285

IS - 5

ER -