New theoretical insights into epoxidation of alkenes by immobilized Mn-salen complexes in mesopores: Effects of substrate, linker and confinement
文献类型：期刊论文
| 作者 | Malek, Kourosh; Li, Can; van Santen, Rutger A. |
| 刊名 | journal of molecular catalysis a-chemical
 |
| 出版日期 | 2007-06-18 |
| 卷号 | 271期号:1-2页码:98-104 |
| 关键词 | enantioselectivity Mn-salen immobilization density functional theory heterogeneous catalysis nanoporous materials chirality |
| 英文摘要 | the origin of enantioselectivity in the epoxidation reaction of cis- and trans-methylstyrene, catalyzed by anchored oxo-mn-v-salen into mcm-41 channels, is investigated by applying density functional calculations in combination with molecular mechanics methodologies. the calculations provide new insights on the importance of electronic and steric effects of the salen ligand, substrate, immobilizing linker and mcm-41 confinement. based on the assumption that the formation of a radical intermediate is the key step along the reaction path, the calculations are performed on a catalytic surface with triplet spin-state, comprising no mn-salen spin-crossing. we rationalize the effect of immobilization and show how that correlates with the linker and substrate choices. we show that although a trans-substrate has a higher level of asymmetric induction to the immobilized mn-salen complex than that to a homogeneous catalyst, the reaction path is more in favor of the cis-substrate. the mcm-41 channel reduces the energy barriers and enhances the enantioselectivity by influencing geometrical distortions of the mn-salen complex. (c) 2007 elsevier b.v. all rights reserved. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, physical |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | enantioselective epoxidation ; heterogeneous catalysis ; mn(salen) catalysts ; olefins ; density |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000246908500018 |
| 公开日期 | 2015-11-17 |
| 源URL | [http://159.226.238.44/handle/321008/140646]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Eindhoven Univ Technol, Schuit Inst Catalysis, ST SKA, NL-5600 MB Eindhoven, Netherlands 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Malek, Kourosh,Li, Can,van Santen, Rutger A.. New theoretical insights into epoxidation of alkenes by immobilized Mn-salen complexes in mesopores: Effects of substrate, linker and confinement[J]. journal of molecular catalysis a-chemical,2007,271(1-2):98-104. |
| APA | Malek, Kourosh,Li, Can,&van Santen, Rutger A..(2007).New theoretical insights into epoxidation of alkenes by immobilized Mn-salen complexes in mesopores: Effects of substrate, linker and confinement.journal of molecular catalysis a-chemical,271(1-2),98-104. |
| MLA | Malek, Kourosh,et al."New theoretical insights into epoxidation of alkenes by immobilized Mn-salen complexes in mesopores: Effects of substrate, linker and confinement".journal of molecular catalysis a-chemical 271.1-2(2007):98-104. |
入库方式： OAI收割
来源：大连化学物理研究所
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