Radical anions of 3,3'-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1'-dioxides in MeCN-H2O solvent mixtures

被引:0
作者
Shundrin, L. A. [1 ]
Irtegova, I. G. [1 ]
Vasil'eva, N. V. [1 ]
Reznikov, V. A. [1 ,2 ]
机构
[1] Russian Acad Sci, Siberian Branch, NN Vorozhtsov Inst Organ Chem, Novosibirsk 630090, Russia
[2] Novosibirsk State Univ, Novosibirsk 630090, Russia
基金
俄罗斯基础研究基金会;
关键词
3,3 '-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1 '-dioxides; cyclic nitrones; dinitrones; radical anions; electrochemical reduction; ESR spectroscopy; DFT; UB3LYP; PCM quantum chemical calculations; 3,3'-BI(2-R-5,5-DIMETHYL-4-OXOPYRROLINYLIDENE) 1,1'-DIOXIDES;
D O I
10.1007/s11172-009-0232-y
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Radical anions of cyclic dinitrones, 3,3'-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1'-dioxides (R = Me, Ph, Bu-t, CF3) have been studied by ESR in combination with quantum chemical calculations of geometrical parameters and isotropic hyperfine interaction constants by the DFT/PBE methods in the 3z basis set and UB3LYP in the 6-31+G* basis set with allowance for the solvation in the framework of continual PCM model. The radical anions were generated electrochemically by reduction of their neutral precursors in MeCN-H2O solvent mixtures and found to possess enough stability for measurement of their ESR spectra in a wide range of the mixture compositions. Radical anions of compounds of nitrone series were generated and characterized in MeCN-H2O mixtures and water (for the dinitrone with R = Me) for the first time. Differences in the solvent depending behavior of the nitrogen hyperfine interaction constants in the series of radical anions with various substituents R are explained by competition of transsolvation and structural effects.
引用
收藏
页码:1681 / 1687
页数:7
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