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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (15): 1528-1536. 上一篇    下一篇

研究论文

9-氯-9-硼芴与NaBH4反应的理论研究

雷依波1, 翟高红*,1, 唐宗薰1, 王育彬2, 文振翼2, 史启祯1   

  1. (1西北大学化学系 陕西省物理无机化学重点实验室 西安 710069)
    (2西北大学现代物理研究所 西安 710069)
  • 投稿日期:2005-12-05 修回日期:2006-02-13 发布日期:2006-08-14
  • 通讯作者: 翟高红

Theoretical Study on the Reaction of 9-Chloro-9-borafluorene and NaBH4

LEI Yi-Bo1, ZHAI Gao-Hong*,1, TANG Zong-Xun1, WANG Yu-Bin2, WEN Zhen-Yi2, SHI Qi-Zhen1   

  1. (1 Department of Chemistry, Shaanxi Key Laboratory of Phsico-Inorganic Chemistry, Northwest University, Xi'an, Shaanxi 710069)
    (2 Institute of Modern Physics, Northwest University, Xi'an, Shaanxi 710069)
  • Received:2005-12-05 Revised:2006-02-13 Published:2006-08-14
  • Contact: ZHAI Gao-Hong

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采用密度泛函理论研究了9-氯-9-硼芴与NaBH4反应的机理, 优化得到了10个中间体和12个过渡态, 并确定了可能的反应通道. 计算结果表明: 主反应通道包含了6个中间体和5个过渡态, 决速步活化能为80.35 kJ•mol－1, 9-硼芴并非反应势能面上最稳定的中间体. 解释了实验上不能成功分离出稳定中间体9-硼芴的原因.

关键词: 9-氯-9-硼芴, NaBH4, DFT, 反应机理

The mechanism of the reaction of 9-chloro-9-borafluorene and NaBH4 has been investigated by density functional theory. The optimized geometries of ten intermediates and twelve transition states were obtained and possible reaction pathways were found. Calculation results indicate that the more possible reaction pathway includes six intermediates and five transition states, the higtest active energy Ea which decides the reaction velocity is 80.35 kJ•mol－1, and that 9-borafluorene is not the most stable intermediate. The reason that the intermediate 9-borafluorene can not be successfully separated experimentally is explained.

Key words: 9-chloro-9-borafluorene, NaBH4, DFT, reaction mechanism