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通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物
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作者 李猛 胡晨晖 +4 位作者 江春涛 杨惠 陈才 侯文华 陈静 《无机化学学报》 SCIE CAS CSCD 北大核心 2013年第11期2339-2346,共8页
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... 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2 h,催化剂用量为0.02 mmol,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(enantiomeric excess,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。 展开更多
关键词 MCM-41 手性mnsalen)配合物 固载型催化剂 不对称环氧化
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Chiral Mn(Ⅲ) salen complex immobilized on imidazole-modified mesoporous material via co-condensation method as an effective catalyst for olefin epoxidation 被引量:1
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作者 LOU LanLan1, YU Yi1, YU Kai2, JIANG Shu1, DONG YanLing1 & LIU ShuangXi1 1 Institute of New Catalytic Materials Science, College of Chemistry, Nankai University, Tianjin 300071, China 2 College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China 《Science China Chemistry》 SCIE EI CAS 2009年第9期1417-1422,共6页
An imidazole modified mesoporous material has been prepared through a co-condensation procedure and adopted to covalently anchor chiral Mn(Ⅲ) salen complex. The active centers in the as-synthesized catalyst were pres... An imidazole modified mesoporous material has been prepared through a co-condensation procedure and adopted to covalently anchor chiral Mn(Ⅲ) salen complex. The active centers in the as-synthesized catalyst were presented in the form of ionic species. The results of XRD, FTIR, DRUV-Vis, and N2 sorp-tion confirmed the successful immobilization of chiral Mn(Ⅲ) salen complex inside the channels of the modified support and the maintenance of the mesoporous structure of parent support in the immobi-lized catalyst. This heterogeneous catalyst exhibited comparable catalytic activity and enantioselectiv-ity to those of the homogeneous counterpart in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, notably high turnover frequencies have been obtained over this heterogeneous catalyst for the relatively short reaction time and low catalyst amount, due in part to the ionic property as well as the uniform distribution of the active centers. 展开更多
关键词 imidazole-functionalized mesoporous material chiral mn(Ⅲ) salen complex CO-CONDENSATION asymmetric EPOXIDATION unfunctionalized OLEFINS
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