• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvation of Sulfur-Centered Cations and Anions in Acetonitrile
【24h】

Solvation of Sulfur-Centered Cations and Anions in Acetonitrile

机译：乙腈中以硫为中心的阳离子和阴离子的溶解

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The solvation of substituted phenylsulfenium ions and thiophenoxides in acetonitrile has been analyzed on the basis of experimental and theoretical data. Experimental solvation energies are obtained from previously reported oxidation and reduction potentials of the corresponding arylthiyl radicals in combination with theoretically calculated ionization potentials and electron affinities at the B3LYP/6-316G(d) level. These calculations provide a consistent set of values in contrast to the data sets obtained in our previous paper (Larsen et al., J. Am. Chem. Soc. 2001, 123, 1723). The extracted solvation data show the expected substituent dependency for both kinds of ions, i.e., the absolute value of the solvation energy decreases as the charge becomes more delocalized. For the thiophenoxides there is good agreement between the experimental solvation energies and solvation energies computed using the polarizable continuum model (PCM). The solvation of the arylsulfenium ions is much stronger than predicted by the PCM method. This can be attributed to the formation of a strong covalent bond of the Ritter type between the arylsulfenium ion and one molecule of acetonitrile. When this interaction is included in the solvation energy calculations by means of a combined supermolecule and PCM approach the experimental data are reproduced within a few kcal mol~(-1). While the energy difference of the singlet and triplet spin states of the arylsulfenium ions is almost negligible in gas phase, the singlet cation is undoubtedly the dominating species in solution, since the triplet cation lacks the ability to form a covalent bond with acetonitrile.
机译：根据实验和理论数据分析了取代的苯基ulf离子和噻吩氧化物在乙腈中的溶剂化作用。从先前报道的相应芳基噻吩基的氧化和还原电势与理论计算的B3LYP / 6-316G（d）电离电势和电子亲和力相结合，可获得实验溶剂化能。与我们之前的论文（Larsen等人，J。Am。Chem。Soc。2001，123，1723）中获得的数据集相比，这些计算提供了一组一致的值。提取的溶剂化数据显示了两种离子的预期取代基依赖性，即，随着电荷变得更局域化，溶剂化能量的绝对值降低。对于噻吩氧化物，实验溶剂化能与使用可极化连续体模型（PCM）计算的溶剂化能之间有很好的一致性。芳基ulf离子的溶剂化作用比PCM方法预测的要强得多。这可以归因于在芳基ion离子和乙腈分子之间形成Ritter型强共价键。当通过结合超分子和PCM方法将这种相互作用包括在溶剂化能的计算中时，实验数据在几千卡mol·（-1）内再现。尽管在气相中芳基ulf离子的单重态和三重态自旋态的能量差几乎可以忽略不计，但单重态阳离子无疑是溶液中的主要物种，因为三重态阳离子缺乏与乙腈形成共价键的能力。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号