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首页> 外文期刊>ChemPlusChem >Selenium-Selenium Bond Cleavage of Diaryl Diselenide Radical Anions During Pulse Radiolysis
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Selenium-Selenium Bond Cleavage of Diaryl Diselenide Radical Anions During Pulse Radiolysis

机译：脉冲辐射过程中的硒 - 硒键粘合杂环纤维细胞的阴离子

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摘要

A selenium-selenium sigma-bond (Se-Se) cleavage of a diaryl diselenide radical anion (ArSeSeAr center dot-) was investigated by absorption measurements during the gamma radiolysis and pulse radiolysis in 2-methyltetrahydrofuran. A di-alpha-naphthyl diselenide radical anion ((NpSeSeNp center dot-)-Np-alpha-Np-alpha) in which an unpaired electron is localized in the Se-Se sigma* orbital between both Se atoms with an elongated Se-Se bond showed an absorption band at 440 nm at 77 K. Upon increasing temperature, the absorption band at 440 nm shifted to 540 nm, thus suggesting that an unpaired electron is delocalized over two naphthalene rings and the Se-Se bond. The disappearance of the absorption band at 540 nm and formation of absorption bands at 420, 620, and 690 nm assigned to the alpha-naphthylselenyl radical were observed during the pulse radiolysis of (NpSeSeNp)-Np-alpha-Np-alpha, thus indicating that the Se-Se bond cleavage occurred in (NpSeSeNp center dot-)-Np-alpha-Np-alpha. The relationship between the Se-Se bond cleavage and delocalization of the unpaired electron in ArSeSeAr center dot- is discussed.
机译：通过在2-甲基四氢呋喃中的γ辐射分解和脉冲辐射分解的吸收测量，研究了硒 - 硒纤维（SE-SE）裂解了二芳基依赖依赖依赖依赖依赖性基团阴离子（Arsesear中心点）的裂解。其中未配对的电子在Se-Se Sigma *轨道中局部化的二甲α-萘基（（NpseseNp中心点 - ） - np-alpha-np-alpha），其在SE原子之间用细长的SE-SE局部地定位键在77k下显示440nm的吸收带。在增加温度时，440nm的吸收带偏移到540nm，因此表明未配对的电子在两个萘环和SE-SE键上划分。在（NPSSENP）-NP-α-NP-α的脉冲辐射分解期间观察到在540nm处的吸收带在540nm处的形成和形成吸收带的吸收带的形成，从而指示SE-SE键裂解发生在（NPSESENP中心DOT - ） - NP-α-NP-α中发生。讨论了arsesear中心点中未配对电子的Se-Se键裂解和取代性之间的关系。

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