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


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
  • 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).


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