...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Why is the antipodal effect in closo-1-SB_9H_9 so large? A possible explanation based on the geometry from the concerted use of gas electron diffraction and computational methods
【24h】

Why is the antipodal effect in closo-1-SB_9H_9 so large? A possible explanation based on the geometry from the concerted use of gas electron diffraction and computational methods

机译：为什么closo-1-SB_9H_9中的对偶作用这么大？气体电子衍射和计算方法的协同使用，基于几何学的可能解释

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 molecular structure of 1-thia-closo-decaborane(9), 1-SB _9H_9, has been determined by the concerted use of gas electron diffraction and quantum-chemical calculations. Assuming C_(4v) symmetry, the cage structure was distorted from a symmetrically bicapped square antiprism (D_(4d) symmetry) mainly through substantial expansion of the tetragonal belt of boron atoms adjacent to sulfur. The S-B and (B-B) _(mean) distances are well determined with r_(h1) = 193.86(14) and 182.14(8) pm, respectively. Geometrical parameters calculated using the MP2(full)/6-311++G** method and at levels reported earlier [MP2(full)/6-311G**, B3LYP/6-311G** and B3LYP/cc-pVQZ], as well as calculated vibrational amplitudes and ~(11)B NMR chemical shifts, are in good agreement with the experimental findings. In particular, the so-called antipodal chemical shift of apical B(10) (71.8 ppm) is reproduced well by the GIAO-MP2 calculations and its large magnitude is schematically accounted for, as is the analogous antipodal chemical shift of B(12) in the twelve-vertex closo-1-SB_(11)H_(11).
机译：1-硫杂-十硼烷（9）1-SB _9H_9的分子结构已通过气体电子衍射和量子化学计算的协同确定。假设C_（4v）对称，笼形结构从对称的双尖方形反棱镜（D_（4d）对称）扭曲，这主要是通过与硫相邻的硼原子的四方带的充分膨胀。分别通过r_（h1）= 193.86（14）和182.14（8）pm可以很好地确定S-B和（B-B）_（平均）距离。使用MP2（完整）/ 6-311 ++ G **方法计算的几何参数，并且以先前报道的水平计算[MP2（完整）/ 6-311G **，B3LYP / 6-311G **和B3LYP / cc-pVQZ] ，以及计算的振动幅度和〜（11）B NMR化学位移，与实验结果非常吻合。尤其是，通过GIAO-MP2计算可以很好地再现所谓的顶端B（10）的对映体化学位移（71.8 ppm），并示意性地解释了其大幅度的变化，就像B（12）的类似对立化学位移一样在十二个顶点closo-1-SB_（11）H_（11）中。

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