| Mechanism and origins of enantioselectivity for [BMIM]Cl ionic liquids and ZnCl2 co-catalyzed coupling reaction of CO2 with epoxides | |
| Department | OSSO国家重点实验室 |
Wang F(王芳) ; Xu CZ(许传芝); Li Z(李臻); Xia CG(夏春谷); Chen J(陈静); Xia CG(夏春谷)
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| 2014 | |
| Source Publication | Journal of Molecular Catalysis A: Chemical
 |
| ISSN | 1381-1169 |
| Volume | 385Pages:133-140 |
| Abstract | Aiming at gaining more insight into the high catalytic activity of ZnCl2/[BMIM]Cl co-catalysts and elucidating the origination about the product enantioselectivity for the coupling reaction of CO2 with epoxides, a mechanistic study has been conducted by performing density functional theory calculations. The calculated results indicate a new stable complex [BMIM]ZnCl3 is probably formed via the dissociation of the in situ generated [BMIM]2ZnCl4 complex in the reaction system. This complex combined with another Cl− jointly assists the break of C—O bond of propylene oxide (PO), which is the rate-determining step for the coupling reaction, and the corresponding barrier (28.0 kcal mol−1) is effectively lowered in comparison with the reaction promoted only by ZnCl2 (65.9 kcal mol−1) or [BMIM]Cl (33.1 kcal mol−1). [BMIM]+ takes part in the reaction by directly or indirectly stabilizing the intermediates and transition states via hydrogen bonding interaction with O of PO or Cl− in the reaction system. The observed product enantioselectivity probably originates from the formation of an interesting intermediate which provides nearly equal opportunities for inserted CO2 to attack the chiral carbon atom of PO on both sides and hence facilitates the formation of both R-product and S-product. |
| Keyword | Mechanism Enantioselectivity Co2 Coupling Reaction Dft ZnCl2/[Bmim]Cl |
| Subject Area | 均相催化 |
| DOI | 10.1016/j.molcata.2014.01.024 |
| Funding Organization | the National Basic Research Pro-gram of China (973 Program, No. 2011CB201404);National Key Technologies R&D Program of China (Project No. 2011BAE17B00);National Natural Science Foundation of China (Project No.21203218) |
| Indexed By | SCI |
| If | 3.615 |
| Language | 英语 |
| Funding Project | 均相催化课题组;分子催化与技术课题组 |
| compositor | 第一作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/5287 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Xia CG(夏春谷) |
| Affiliation | Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China |
| Recommended Citation GB/T 7714 | Wang F,Xu CZ,Li Z,et al. Mechanism and origins of enantioselectivity for [BMIM]Cl ionic liquids and ZnCl2 co-catalyzed coupling reaction of CO2 with epoxides[J]. Journal of Molecular Catalysis A: Chemical,2014,385:133-140. |
| APA | Wang F,Xu CZ,Li Z,Xia CG,Chen J,&夏春谷.(2014).Mechanism and origins of enantioselectivity for [BMIM]Cl ionic liquids and ZnCl2 co-catalyzed coupling reaction of CO2 with epoxides.Journal of Molecular Catalysis A: Chemical,385,133-140. |
| MLA | Wang F,et al."Mechanism and origins of enantioselectivity for [BMIM]Cl ionic liquids and ZnCl2 co-catalyzed coupling reaction of CO2 with epoxides".Journal of Molecular Catalysis A: Chemical 385(2014):133-140. |
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| Mechanism and origin（1290KB） | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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