Features of Mechanism of Cycloaddition Reaction between Me2Ge=Sn: and Ethylene
谭晓军;卢秀慧;谷劲松
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)
Features of Mechanism of Cycloaddition Reaction between Me2Ge=Sn: and Ethylene
TAN Xiao-Jun;LU Xiu-Hui;GU Jin-Song
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)
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 p-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 p → 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 p → 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.
Abstract：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 p-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 p → 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 p → 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.
基金资助:Supported by the National Natural Science Foundation of China (No. 31370090) and Project of Key R&D of Shandong Province (No. 2015GSF121006)
通讯作者:
lxh@ujn.edu.cn
E-mail: lxh@ujn.edu.cn
引用本文:
谭晓军;卢秀慧;谷劲松. Features of Mechanism of Cycloaddition Reaction between Me2Ge=Sn: and Ethylene[J]. 结构化学, 2020, 39(9): 1627-1632.
TAN Xiao-Jun;LU Xiu-Hui;GU Jin-Song. Features of Mechanism of Cycloaddition Reaction between Me2Ge=Sn: and Ethylene. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(9): 1627-1632.
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