物理化学学报 >> 2016, Vol. 32 >> Issue (6): 1434-1438.doi: 10.3866/PKU.WHXB201603101

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包含ptC的Au(I)配合物催化烯丙基醋酸盐重排反应的理论研究

贾晓芳,张聪杰*()   

  • 收稿日期:2016-01-15 发布日期:2016-06-03
  • 通讯作者: 张聪杰 E-mail:zcjwh@snnu.edu.cn
  • 基金资助:
    国家自然科学基金(21373133)

A Theoretical Investigation of the Rearrangement Reaction of Allylic Acetates Catalyzed by Au(I) Complexes with PtC

Xiao-Fang JIA,Cong-Jie ZHANG*()   

  • Received:2016-01-15 Published:2016-06-03
  • Contact: Cong-Jie ZHANG E-mail:zcjwh@snnu.edu.cn
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(21373133)

摘要:

理论上,采用密度泛函理论研究两类包含平面四配位碳的Au(I)配合物([Au(C3H2BR)]+, R = Me, t-Bu)催化烯丙基醋酸盐的重排反应。计算结果表明,配合物[Au(C3H2BR)]+催化烯丙基醋酸盐重排反应相比较文献中报道的催化剂[Au(NHC)]+而言,能垒降低了9.2-11.7 kJ.mol-1。因此,除了配体CO和NHC之外,配合物[Au(C3H2BR)]+中的新型配体将会在配位化学以及有机化学中具有应用潜力。

关键词: 密度泛函理论, 金属, 平面四配位碳, 催化, 重排反应

Abstract:

The rearrangements of allylic acetates catalyzed by [Au(C3H2BR)]+ (R = Me, t-Bu) with planar tetracoordinate carbon (ptC) have been theoretically investigated. Calculated results show that the free energy barriers and the reaction free energies of the [Au(C3H2BR)]+-catalyzed rearrangement of allylic acetates are lower than those using [Au(NHC)]+ by 9.2-11.7 kJ.mol-1, indicating that a third type of containing C-terminal ligand besides CO and NHC might have potential applications in coordination and organic chemistry as well.

Key words: Density functional theory, Metal, Planar tetracoordinate carbon, Catalysis, Rearrangement reaction

MSC2000: 

  • O641