| 通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物 | |
| Immobilization of Chiral Mn(salen) Complex on MCM-41 via Functionalizing with Benzyl Sulphonic Acid | |
| 摘要: 首先通过两步后合成处理,在MCM-41上接枝苄基磺酸;然后,以苄基磺酸为过渡产物,用手性Mn(salen)配合物修饰处理,得到了苄基磺酸轴向负载手性Mn(salen)配合物的MCM-41;实现了在廉价且温和条件下均相手性Mn(salen)催化剂的非均相化。采用X射线衍射(XRD)、低温N2吸附-脱附、红外光谱、热重-差示扫描量热(TG-DSC)分析、电感耦合等离子体发射光谱(ICP)和酸度滴定等对样品进行了表征。结果表明,手性Mn(salen)配合物成功固载在MCM-41上,且MCM-41的介孔结构和Mn(salen)配合物的手性特征仍然保留。以间氯过氧苯甲酸为氧化剂,考察了所得固载型催化剂对α-甲基苯乙烯的不对称环氧化催化性能,结果表明在0℃反应2h,催化剂用量为0.02mmol,无需加入轴向配体N-甲基吗啉氮氧化物(NMO)的条件下对映体过量(enantiomericexcess,e.e.)值可达99%以上,转化率为77%。归因于苄基磺酸基起到了很好的轴向配体作用。经适当处理,固载型催化剂在循环使用5次后e.e.值依然有71%,表现出较好的活性和重复使用性能。 | |
| 关键词: MCM-41 手性Mn(salen)配合物 固载型催化剂 不对称环氧化 | |
| 基金项目: 国家自然科学基金(No.21073084);江苏省自然科学基金(BK2011438);国家基础研究973项目(2009CB623504);南京工业大学青年教师学术基金(No.39704013)资助项目。 | |
| Abstract: MCM-41 was first functionalized with benzyl sulphonic acid using a post-synthetic procedure and then modified with chiral Mn(salen) complex to prepare a heterogeneous chiral Mn(salen) catalyst under cheap and mild conditions. The chiral Mn(salen) complex was axially immobilized into MCM-41 via the organic benzyl sulfonic groups. The catalyst was characterized by XRD, N2 adsorption-desorption, FTIR, TG-DSC, ICP and acid capacity titration. The results show that the chiral Mn(salen) complex has been supported on MCM-41, and the mesoporous structure of MCM-41 and the chiral structure of Mn(salen) are still remained. The supported catalyst was applied to the asymmetric epoxidation of α-methylstyrene using m-chloroperbenzoic acid as an oxidant at 0 ℃, and showed excellent performance with a conversion of 77% and e.e. (enantiomeric excess) value above 99% after a rather short reaction time of 2 h in the absence of NMO (N-Methylmorpholine-N-Oxide). The benzyl sulphonic acid groups play a very good axial ligand function. By treating properly, the e.e. value was still 71% after the supported catalyst was reused 5 times. | |
| Keywords: MCM-41 chiral Mn(salen) complex supported catalyst asymmetric epoxidation | |
| 投稿时间：2013-03-31 修订日期：2013-06-28 | |
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| 李猛,胡晨晖,江春涛,杨惠,陈才,侯文华,陈静.通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物[J].无机化学学报,2013,29(11):2339-2346. | |
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