SUBSTITUENT EFFECTS ON THE STABILITY OF 3-ELECTRON-BONDED RADICALS AND RADICAL IONS FROM ORGANIC SULFUR-COMPOUNDS
SUBSTITUENT EFFECTS ON THE STABILITY OF 3-ELECTRON-BONDED RADICALS AND RADICAL IONS FROM ORGANIC SULFUR-COMPOUNDS
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DOI：
10.1021/ja00332a039
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发表时间：
1984-01-01
影响因子：
15
通讯作者：
ASMUS, KD
中科院分区：
文献类型：
--
作者：
GOBL, M;BONIFACIC, M;ASMUS, KD
测量了各种（R ~ 2S.）SR2）+，（RS/. SR）-、R2S/.溴自由基和自由基离子的脉冲辐解技术。结果证实，这些物种的光学性质是一个敏感的措施，其三电子（2，1*）键的强度。Xmax的相当大的红移与取代基R的诱导能力平行。这可以用电子被引入反键 * 轨道而导致的键弱化来解释。线性自由能相关性使我们能够量化的诱导effectand，此外，以评估空间位阻的影响，对稳定性的三电子bonds.The形成的三电子键合的自由基，其特征在于由一个相对较弱的键之间的两个杂原子已经建立在近年来在一些液体和固体状态的研究。典型的例子是（R2 S/. SR2）+、1-9（R2Se/. SeR2）V（> N/. N<）+、11-13和（> S/. N<）+ 14· 15自由基
Optical absorption spectra have been measured for a variety of (R2S.\SR2)+,(RS/. SR)-, R2S/. Br radicalsand radical ions by using pulse radiolysis techniques. The results substantiate that the optical properties of such species are a sensitive measure for the strength of their three-electron (2, 1*) bonds. A considerable red shift in Xmax parallels the inductive power of the substituents R. This is explained by bond weakening due to electron induction into the antibonding* orbital. Linear free energy correlations allow us to quantify the inductive effectand, in addition, to evaluate the influence of steric hindrance on the stability of the three-electron bonds.The formation of three-electron-bonded radicals which are characterized by a relatively weak bondbetween two hetero atoms has been well established over recent years in several liquid-and solid-state studies. Typical examples are(R2S/. SR2)+, 1-9 (R2Se/. SeR2) V (> N/. N<)+, 11-13 and (> S/. N<)+ 14· 15 radical