物理化学学报 >> 2011, Vol. 27 >> Issue (03): 571-576.doi: 10.3866/PKU.WHXB20110312

理论与计算化学 上一篇    下一篇

(Cl-nacnac)Pt(H)与端炔的反应机理

王家勇, 毕思玮, 赵俊凤   

  1. 曲阜师范大学化学与化工学院, 山东 曲阜 273165
  • 收稿日期:2010-10-27 修回日期:2010-12-27 发布日期:2011-03-03
  • 通讯作者: 毕思玮 E-mail:siweibi@126.com
  • 基金资助:

    山东省自然科学基金(Y2007B23)和固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目

Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne

WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng   

  1. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China
  • Received:2010-10-27 Revised:2010-12-27 Published:2011-03-03
  • Contact: BI Si-Wei E-mail:siweibi@126.com
  • Supported by:

    The project was supported by the Natural Science Foundation of Shandong Province, China (Y2007B23) and State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, China (200702).

摘要:

在Templeton实验(West, N. M.; et al. Organometallics 2008, 27, 5252)的基础上, 利用密度泛函理论研究了(Cl-nacnac)Pt(H)(Cl-nacnac: bis(N-aryl)-β-diiminate)与端炔的主、副反应机理. 结果表明: 叔丁基乙炔以1,2-方式插入到Pt―H键之间生成主产物, C―C键生成为决速步骤; 以2,1-方式插入到Pt―H键之间生成副产物, 炔烃插入为决速步骤. 基于主、副反应机理, 合理地解释了主、副产物生成的原因. 分析表明, 主产物是热力学控制的产物, 而副产物是动力学控制的产物.

关键词: 密度泛函理论, 反应机理, 铂, 炔烃插入, 炔烃双聚

Abstract:

On the basis of Templeton′s experiment (West, N. M.; et al. Organometallics 2008, 27, 5252), the mechanisms of the main and the side reactions between (Cl-nacnac)Pt(H) (Cl-nacnac: bis(N-aryl)- β-diiminate) and a terminal alkyne were investigated by density functional theory. Our study shows that the 1,2-insertion of t-BuC≡CH into the Pt―H bond generates the main products and that C―C bond formation is the rate-determining step. The 2,1-insertion of t-BuC≡CH into the Pt―H bond generates the by- products and alkyne insertion is the rate-determining step. Based on the mechanisms of the main and side reactions the presence of the main product and the by-product could be explained. We found that the main product is thermodynamically controlled while the side product is kinetically controlled.

Key words: Density functional theory, Reaction mechanism, Pt, Alkyne insertion, Alkyne dimerization

MSC2000: 

  • O641