Citation: ZHU Yuan-Qiang, GUO Jian-Chun, YE Zhong-Bin. AuCl_x (x=1, 3)-Catalyzed Benzannulation Mechanisms between 2-Propynyl-hypnone and Benzyne[J]. Acta Physico-Chimica Sinica, ;2011, 27(09): 2043-2050. doi: 10.3866/PKU.WHXB20110921 shu

AuCl_x (x=1, 3)-Catalyzed Benzannulation Mechanisms between 2-Propynyl-hypnone and Benzyne

1.
1. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Chemistry and Chemical Engineering,Southwest Petroleum University, Chengdu 610500, P. R. China;
2. School of Petroleum Engineering, Southwest PetroleumUniversity, Chengdu 610500, P. R. China

Received Date: 9 May 2011
Available Online: 14 July 2011
Fund Project: 四川省教育厅科研项目(09ZB099)资助 (09ZB099)

The AuCl_x (x=1, 3)-catalyzed benzannulation mechanisms between benzyne and 2-propynylhypnone were investigated using B3LYP, B3PW91, UB3LYP, and the second-order Møller-Plesset perturbation (MP2) methods with the LanL2DZ basis set for Au and the 6-31G^*, 6-311++G^** basis sets for C, H, O, Cl. For the AuCl or AuCl₃ catalysts the reaction occurs through both the [4 + 2] and the [3 + 2] benzannulation pathways to yield the product. With AuCl, the reaction occurs mainly through the [4 + 2] reaction pathway because of this pathway's low activation free energy. With AuCl₃, the reaction occurs by the [4+2] and the [3+2] reaction pathways. These two pathways are competitive because of their close activation free energies. An analysis of these results indicates that the ld oxidation states change the reaction mechanisms and greatly influence the reaction barriers. The calculated results indicate that the AuCl catalyst is more effective than AuCl₃ because in the reaction catalyzed by AuCl the activation free energy of the rate determining step is 11.18 kJ·mol^-1 lower than that of the reaction catalyzed by AuCl₃. These results are in od agreement with the experimental observations.
- ld catalyst,
- Density functional theory,
- Reaction mechanism,
- [4+2] Benzannulation,
- [3+2] Benzannulation
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沈阳化工大学材料科学与工程学院沈阳 110142

AuClx (x=1, 3)-Catalyzed Benzannulation Mechanisms between 2-Propynyl-hypnone and Benzyne

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通讯作者: 陈斌, bchen63@163.com

AuCl_x (x=1, 3)-Catalyzed Benzannulation Mechanisms between 2-Propynyl-hypnone and Benzyne