(Cl-nacnac)Pt(H)与端炔的反应机理

doi:10.3866/PKU.WHXB20110312

Abstract

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

WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng. Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne[J].Acta Phys. -Chim. Sin., 2011, 27(03): 571-576.

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

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