• 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 >Gaseous Trihalogen Cations. Formation, Structure and Reactivity of Cl_3~+ and Cl_2F~+ Ions from a Joint ab Initio and FT-ICR Study
【24h】

Gaseous Trihalogen Cations. Formation, Structure and Reactivity of Cl_3~+ and Cl_2F~+ Ions from a Joint ab Initio and FT-ICR Study

机译：气态三卤素阳离子。从头算和FT-ICR联合研究Cl_3〜+和Cl_2F〜+离子的形成，结构和反应性

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

Gaseous Cl_3~+ ions were obtained by two convenient routes, namely. Cl~+ transfer to chlorine from Cl_3H~+ or Cl_2~+ ions, whereas Cl_3F~+ was prepared upon fluorination of chlorine by XeF~+. The structure and the stability of the trihalogen cations were investigated by reactive probing, utilizing FTICR mass spectrometry to survey their reactivity, in particular Cl~+ transfer processes toward selected nucleophiles. The structure, relative stability, and dissociation enthalpies of Cl_3~+ and Cl_2F~+ wee investigated by computational methods based on density functional theory up to the CCSD(T)/cc-p VQZ//B2LYP/6-311++G(3df, 3pd) level. The results show that an A_1 singlet of C_(2v) symmetry is the global minimum on the Cl_3~+ potential energy surface. Consistent with earlier results, the asymmetric bent (Cl-Cl-F)~+, also an A_1 singlet, is more stable by 44.3 kcal mol~(-1) at 298 K than the symmetric isomer of (Cl-F-Cl)~+ connectivity. By combining theoretically computed dissociation enthalpies with available thermochemical data the heats of formation of Cl_3~+ and Cl_2F~+ cations, in their ground state, can be estimated to be 251.5+-5 and 245.0+-5 kcal mol~(-1) at 298 K. Comparison of the Cl~+ and F~+ binding energies to simple halogenated molecules shows an excellent linear correlation, which is not the case when the comparison is extended to the proton affinities. The different factors that influence the stability of protonated and halogenated adducts are briefly discussed.
机译：气态Cl_3〜+离子是通过两种简便的途径获得的。 Cl〜+从Cl_3H〜+或Cl_2〜+离子转变成氯，而Cl_3F〜+由XeF〜+氟化氯制得。三卤素阳离子的结构和稳定性通过反应探针法进行了研究，利用FTICR质谱法研究了它们的反应性，特别是向选定亲核体的Cl〜+转移过程。基于密度泛函理论的计算方法研究了Cl_3〜+和Cl_2F〜+的结构，相对稳定性和离解焓，直至CCSD（T）/ cc-p VQZ // B2LYP / 6-311 ++ G（ 3df，3pd）级别。结果表明，C_（2v）对称的A_1单线态是Cl_3〜+势能面上的全局最小值。与较早的结果一致，非对称弯曲（Cl-Cl-F）〜+，也是A_1单线态，在（298）K下比（Cl-F-Cl）的对称异构体稳定44.3 kcal mol〜（-1）。 〜+连接。通过将理论计算的解离焓与可用的热化学数据结合，在基态下，Cl_3〜+和Cl_2F〜+阳离子的形成热可估计为251.5 + -5和245.0 + -5 kcal mol〜（-1）在298 K时，Cl〜+和F〜+结合能与简单卤代分子的比较显示出极好的线性相关性，当比较范围扩展到质子亲和力时，情况并非如此。简要讨论了影响质子化和卤化加合物稳定性的不同因素。

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