Citation: WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng. Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne[J]. Acta Physico-Chimica Sinica, ;2011, 27(03): 571-576. doi: 10.3866/PKU.WHXB20110312 shu

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

1.
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China

Received Date: 27 October 2010
Available Online: 27 January 2011
Fund Project: 山东省自然科学基金(Y2007B23) (Y2007B23)固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目 (厦门大学)(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.
- Density functional theory,
- Reaction mechanism,
- Pt,
- Alkyne insertion,
- Alkyne dimerization
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