| OxoMn(Salen)与取代乙烯的环氧化反应机理的理论研究 |
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| 引用本文： | 王长生,汤立鹏,曲威,李书实,赵明,张丹.OxoMn(Salen)与取代乙烯的环氧化反应机理的理论研究[J].辽宁师范大学学报(自然科学版),2010,33(3). |
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| 作者姓名： | 王长生 汤立鹏 曲威 李书实 赵明 张丹 |
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| 作者单位： | 辽宁师范大学化学化工学院,辽宁,大连,116029 |
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| 基金项目： | 国家自然科学基金项目 |
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| 摘 要： | 使用B3LYP方法研究了OxoMn(Salen)与取代乙烯CH2=CHR(R=H,Me,NO2,CF3)的环氧化反应机理.结果表明:OxoMn(Salen)与取代乙烯的反应不可能经由协同反应通道完成;由于第一过渡态的相对Gibbs自由能太高,单重态OxoMn(Salen)与取代乙烯的反应也不可能经由分步反应通道完成;三重态和五重态OxoMn(Salen)与取代乙烯的反应可以经由分步反应通道2步完成,并且第1步是反应的决速步骤.研究结果还表明,取代基对第一过渡态的相对Gibbs自由能影响不大.
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| 关 键 词： | 环氧化反应 取代乙烯 相对Gibbs自由能 |
Theoretical study on the epoxidation reaction mechanism between substituted ethylenes and the OxoMn(Salen)complex |
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| WANG Chang-sheng,TANG Li-peng,QU Wei,LI Shu-shi,ZHAO Ming,ZHANG Dan.Theoretical study on the epoxidation reaction mechanism between substituted ethylenes and the OxoMn(Salen)complex[J].Journal of Liaoning Normal University(Natural Science Edition),2010,33(3). |
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| Authors: | WANG Chang-sheng TANG Li-peng QU Wei LI Shu-shi ZHAO Ming ZHANG Dan |
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| Institution: | WANG Chang-sheng,TANG Li-peng,QU Wei,LI Shu-shi,ZHAO Ming,ZHANG Dan(School of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029,China) |
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| Abstract: | Theoretical studies based on a hybrid density functional theory(B3LYP)were carried out to explore the epoxidation reaction mechanism between substituted ethylenes CH2=CHR(R=H,Me,NO2,CF3)and the OxoMn(Salen)complex.Calculation results show that the reactions could not follow through a concerted mechanism.The reactions in the singlet energy hyper surface could not accomplish through a stepwise pathway either,owing to the high relative Gibbs free energies in the first transition states process.The stepwise pat... |
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| Keywords: | epoxidation substituted ethylene relative Gibbs free energies |
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