物理化学学报 >> 2009, Vol. 25 >> Issue (12): 2501-2506.doi: 10.3866/PKU.WHXB20091205

研究论文 上一篇    下一篇

(BCO)12与(CH)12稳定性的环张力分析

崔小英, 贾建峰, 杨斌盛, 武海顺   

  1. 山西大学分子科学研究所, 太原 030006; 山西师范大学化学与材料科学学院, 山西 临汾 041004
  • 收稿日期:2009-06-08 修回日期:2009-09-01 发布日期:2009-11-27
  • 通讯作者: 武海顺 E-mail:wuhs@mail.sxnu.edu.cn

Stability Comparison between (BCO)12 and (CH)12 by Ring Strain Analysis

CUI Xiao-Ying, JIA Jian-Feng, YANG Bin-Sheng, WU Hai-Shun   

  1. Institute of Molecular Science, Shanxi University, Taiyuan 030006, P. R. China; School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004, Shanxi Province, P. R. China
  • Received:2009-06-08 Revised:2009-09-01 Published:2009-11-27
  • Contact: WU Hai-Shun E-mail:wuhs@mail.sxnu.edu.cn

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摘要：

基于密度泛函理论的B3LYP方法, 对具有等瓣相似性的(BCO)12和(CH)12的10种异构体结构的稳定性进行了计算对比研究, 这10种异构体由三元、四元、五元和六元环组成. 环张力分析表明对羰基硼笼体系, 三元环起主要的稳定化作用, 而四元环是张力的主要来源, 对碳氢笼体系, 五元环起主要的稳定化作用. 电子差分密度表明羰基硼笼中的三元环与碳氢笼中的三元环有不同的电子结构, 导致了它们不同的张力表现. 核独立化学位移(NICS)分析表明, 尽管σ芳香性不是稳定性的决定因素, 但对笼的稳定性有一定的影响.

关键词: 稳定性, 羰基硼, 碳氢笼, 张力环, 核独立化学位移

Abstract:

Based on the B3LYP method of density functional theory, a stability comparison between the 10 isomers of isolobal (BCO)12 and (CH)12, which comprise three-membered, four-membered, five-membered, and six-membered rings, was undertaken. Ring strain analysis indicates that the three-membered ring can stabilize the boron carbonyl cage while the four-membered ring destabilizes it. For the hydrocarbon cage, the five-membered ring is most stable. Electronic difference density analysis reveals that the three-membered rings of the boron carbonyl cage have different electronic structures from those of the hydrocarbon cage. Therefore, they have different ring strains. Nucleus-independent chemical shifts (NICS) analysis indicates that σ-aromaticity can affect the stabilities of (BCO)12 and (CH)12 cages although this is not decisive.

Key words: Stability, Boron carbonyl, Hydrocarbon cage, Strained ring, Nucleus-independent chemical shift