Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (03): 571-576.doi: 10.3866/PKU.WHXB20110312

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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