Citation: Xiao-Jun TAN, Xiu-Hui LU, Jin-Song GU. Features of Mechanism of Cycloaddition Reaction between Me₂Ge=Sn: and Ethylene[J]. Chinese Journal of Structural Chemistry, ;2020, 39(9): 1627-1632. doi: 10.14102/j.cnki.0254-5861.2011-2667 shu

Features of Mechanism of Cycloaddition Reaction between Me₂Ge=Sn: and Ethylene

a.
School of Biological Science and Technology, University of Jinan, Jinan 250022, China
b.
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China

Corresponding author: Xiu-Hui LU, lxh@ujn.edu.cn Jin-Song GU, jndxswxygjs@163.com
Received Date: 15 November 2019
Accepted Date: 1 April 2020

Fund Project: the National Natural Science Foundation of China 31370090Project of Key R & D of Shandong Province 2015GSF121006

Figures(5)

X₂Ge=Sn: (X = H, Me, F, Cl, Br, Ph, Ar···) are new species of chemistry. The cycloaddition reaction of X₂Ge=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X₂Ge=Sn: and the symmetric π-bonded compounds, the cycloaddition reactions of Me₂Ge=Sn: and ethylene were selected as model reactions in this paper, and the mechanism was investigated for the first time here using the MP2 theory together with the 6-311++G** basis set for C, H and Ge atoms and the LanL2dzbasis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule present is that the 5p unoccupied orbital of Sn in Me₂Ge=Sn: and the π orbital of ethylene form a π → p donor–acceptor bond, resulting in an intermediate which, due to its instability, makes itself isomerize into a four-membered Ge-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Ge-heterocyclic ring stannylene and the π orbital of ethylene form a π → p donor-acceptor bond, the four-membered Ge-heterocyclic ring stannylene further combines with ethylene to get another intermediate. Because the Sn atom in this intermediate exhibits sp³ hybridization after transition state, the intermediate isomerizes to a Ge-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X₂Ge=Sn: and the symmetric π-bonded compounds. This study opens up a new research field for stannylene chemistry.
- Me₂Ge=Sn:,
- cycloaddition reaction,
- molar Gibbs free energy of reaction (Δ_rG_m),
- potential energy profile
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Features of Mechanism of Cycloaddition Reaction between Me2Ge=Sn: and Ethylene

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通讯作者: 陈斌, bchen63@163.com

Features of Mechanism of Cycloaddition Reaction between Me₂Ge=Sn: and Ethylene