Influence of delocalization on the stability of dianions: study of a systematic series of dianions with growing electronic localization.
Influence of delocalization on the stability of dianions: study of a systematic series of dianions with growing electronic localization.
复制标题
离域对二价阴离子稳定性的影响：对电子局域化不断增长的一系列系统性二价阴离子的研究。
DOI：
10.1021/ja035878f
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发表时间：
2003
影响因子：
15
通讯作者：
L. Cederbaum
中科院分区：
文献类型：
--
作者：
Sven Feuerbacher;L. Cederbaum
双阴离子的电子稳定性受其电子离域程度的影响，但通常不可能将这种影响与其他影响分开。在这里，我们通过理论手段研究了由 phen-1,4-ylenbis(ethynide) 及其七种衍生物组成的双阴离子序列，这些衍生物是通过几个步骤氢化苯核而获得的。这些双阴离子结构相似，主要区别在于其电子的离域程度。我们提出了在相关理论水平上计算的几何形状和电子脱离能量。结果表明，八种双阴离子可分为三组不同的电子稳定性。我们能够通过简单的共振结构图来解释这种分组，这说明了为什么具有更多离域电子的双阴离子不太稳定。
The electronic stability of a dianion is influenced by the degree of delocalization of its electrons, but it is generally not possible to separate this influence from other effects. Here, we investigate by theoretical means the sequence of dianions consisting of phen-1,4-ylenbis(ethynide) and seven of its derivatives obtained by hydrogenating the benzene core in several steps. These dianions are structurally similar and mainly differ by the degree of delocalization of their electrons. We present geometries and electron detachment energies computed at a correlated level of theory. The results point to a classification of the eight dianions in three distinct groups of electronic stability. We are able to explain this grouping by a simple resonance structure picture, which demonstrates why the dianions with more delocalized electrons are less stable.