高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (7): 1625-1630.doi: 10.7503/cjcu20200106

• 物理化学 • 上一篇    下一篇

平面四配位和五配位的B6S5团簇

王艺桥,王聪,刘兴满,张珉(),耿允,赵亮()   

  1. 东北师范大学化学学院功能材料化学研究所, 长春 130024
  • 收稿日期:2020-03-02 出版日期:2020-07-10 发布日期:2020-05-09
  • 通讯作者: 张珉,赵亮 E-mail:mzhang@nenu.edu.cn;zhaoliang@nenu.edu.cn
  • 基金资助:
    国家自然科学基金(21673036);中央高校基本科研业务经费(2412018ZD006)

Planar Tetracoordinate Boron and Pentacoordinate Boron in B6S5 Clusters

WANG Yiqiao,WANG Cong,LIU Xingman,ZHANG Min(),GENG Yun,ZHAO Liang()   

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2020-03-02 Online:2020-07-10 Published:2020-05-09
  • Contact: ZHANG Min,ZHAO Liang E-mail:mzhang@nenu.edu.cn;zhaoliang@nenu.edu.cn
  • Supported by:
    † National Natural Science Foundation of China(21673036);Fundamental Research Funds for the Central Universities, China(2412018ZD006)

摘要:

采用B3LYP/def2-TZVP优化和在耦合簇方法(CCSD)单点水平下, 将$B_{6}S^{n}_{5}$ (n=0, +1, +2)作为基础结构研究证实了S原子对于形成B平面多配位结构具有良好的作用. 研究发现, $B_{6}S^{n}_{5}$ (n=0, +1, +2) 3种价态下最稳定和次稳定结构均为纯平面结构, 仅在不同电子数下两者的能量次序发生改变. 中性的B6S5因满足18电子规则其最稳定结构具有D5h对称性, 且中心B为平面五配位. 在$B_{6}S^{+}_{5}$和$B_{6}S^{2+}_{5}$中, 其17电子和16电子时的最稳定结构中的所有B均为平面四配位. 18电子的B6S5更为稳定.

关键词: $B_{6}S^{n}_{5}$ (n=0,+1+2), 平面四配位, 平面五配位, 芳香性, 硫桥连

Abstract:

At the level of B3LYP/def2-TZVP optimization and CCSD single point energy, $B_{6}S^{n}_{5}$ (n=0, +1, +2) was utilized to validate the valuable effect of peripheral sulfur atom on constructing planar coordinated boron. The structures of global energy minimum(GEM) and the second lowest energy minimum in three charge states are purely planar ones, and their structures are very similar. Only their order is exchanged with the loss of the electrons. There exists a planar pentacoordinate boron in the GEM structure of D5h-B6S5 due to the 18 electron rule, and there are all the planar tetracoordinate borons in the GEM structure of $B_{6}S^{n}_{5}$ (n=0, +1, +2). Meanwhile, the sulfur-bridging bonding is another key factor to maintain their planar molecular structures.

Key words: $B_{6}S^{n}_{5}$ (n=0,+1+2), Planar tetracoordinate, Planar pentacoordinate, Aromaticity, Sulfur bridge

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