Asymmetric epoxidation of unfunctionalized olefins catalyzed by Mn(III) salen complex immobilized on MCM-48

Chiral Mn(III) salen complexes were supported on mesoporous molecular sieve MCM-48 and employed as catalyst in the asymmetric epoxidation of some unfunctionalized olefins. The as-synthesized catalysts showed excellent enantioselectivity than homogeneous catalysts for α-methylstyrene and the highest ee value (up to >99%) was obtained. Furthermore, these catalysts were also effective for bulkier olefins such as indene and 1-phenylcyclohexene. Compared to homogeneous counterparts, the heterogeneous catalysts are more stable and can be recycled three times without loss of enantioselectivity.     

The catalytic activity of new chiral salen complexes immobilized on MCM-41 in the asymmetric hydrolysis of epoxides to diols

The synthesis of MCM-41 type mesoporous material has been performed by the solvent evaporation method. The chiral salen Co(III)(OAc) complexes are immobilized on a siliceous MCM-41 through the multi-step anchoring and applied as catalysts in the hydrolytic kinetic resolution of racemic epoxides to diols. The incorporation of salen complexes onto the mesoporous material is demonstrated by UV–Vis spectroscopy, and tested with the catalytic hydrolysis reaction. The chiral salen Co(III) complexes catalyze the hydrolysis of epichlorohydine, 1,2-epoxyhexane, epoxystyrene and epoxycyclohexane under very mild conditions. This reaction can proceed in acetonitrile and THF solvents.     

A new and easy method for anchoring manganese salen on MCM-41

This work reports a new method to covalently attach manganese salophen complex onto MCM-41, using a diisocyanate as a binder. The prepared catalyst was tested on the liquid phase limonene oxidation reaction. Diluted t-Butyl hydroperoxide was used as oxygen supplier. Limonene oxide, carveol and carvone are formed, but the main product obtained was a polymer. The preservation of the MCM-41 channel system was checked by X-ray diffraction and nitrogen adsorption analysis. The use of the same catalyst sample in four consecutive experiments, without loss of activity, is a confirmation of the success of the anchoring process.     

Preparation of MCM-41 Supported Heterogenized Chiral Salen Mn (III) Complex and the Catalytic Activity in the Asymmetric Epoxidation

A chiral Manganese (III) salen complex was immobilized on the walls of MCM-41 (mobile crystalline material) through the multi-grafting method. The immobilized complex was characterized by XRD, FTIR, UV-Vis, ICP and Nitrogen sorption, and was applied to the asymmetric epoxidation of unfuctionalized alkenes including 1,2-dihydronaphthalene, α-methylstyrene, cis-β-methylstyrene, styrene using NaClO and m-chloroperbenzoic acid (m-CPBA) as oxidants respectively. The immobilized complex showed good activity and enantioselectivity in the epoxidation of 1,2-dihydronaphthalene by using NaClO as oxidant. It could also be run for 4 times in the epoxidation of α-methylstyrene without obvious loss of activity or enantiomeric excess.     

Mn(Salen)/Al-MCM-41的微波固相法制备及其表征

报道了一种新的微波固相法制备Mn(Salen)/Al-MCM-41催化剂的方法,并与常规制备方法进行了比较。对微波固相法制备的催化剂进行了一系列的表征,表征结果表明,微波固相方法和常规方法均能成功地将Mn(Salen)络合物固载于介孔Al-MCM-41分子筛中,且在原料的量相同的情况下,红外光谱显示微波固相法具有更强的吸收峰。比较了不同方法制备的催化剂在苯乙烯环氧化反应中的催化性能,发现微波固相法制备的Mn(salen)/Al-MCM-41-IP催化剂具有较高的催化活性和最好的环氧化物选择性。还考察了催化剂性能与制备过程中的微波辐射时间的关系。进行了催化剂的重复使用的实验,使用三次后,转化率达到59.4%,选择性可达78.3%。     

Effect of pore size on the performance of mesoporous material supported chiral Mn(III) salen complex for the epoxidation of unfunctionalized olefins

A series of mesoporous MCM-41 and MCM-48 materials with different pore sizes were synthesized and used as supports to immobilize chiral Mn(III) salen complex. The heterogeneous catalysts were characterized by XRD, FT-IR, DR UV–vis, and N₂ sorption, and the results indicated the successful immobilization of chiral Mn(III) salen complex. The confinement effect of pore size on the catalytic performance of the heterogeneous catalysts was studied for the asymmetric epoxidation of unfunctionalized olefins with m-chloroperoxybenzoic acid as an oxidant. It was found that the conversions and enantiomeric excess (ee) values were closely correlated with the pore sizes of parent supports. The catalysts immobilized on the large-pore mesoporous supports exhibited higher conversions, and for the catalysts immobilized on MCM-41 materials, the ee values improved with increasing pore size. However, for the MCM-48 material-supported catalysts, the compatible pore size of the support with the substrate was beneficial for obtaining higher enantioselectivity in olefin epoxidation.     

Catalytic Oxidation of Alkylaromatics over Mesoporous (Cr)MCM-41

Liquid-phase catalytic oxidation of certain alkylaromatics over mesoporous (Cr)MCM-41 molecular sieves in the presence of chlorobenzene and tertiary butylhydroperoxide showed high substrate conversion and excellent product selectivity. The high catalytic activity of the materials is attributed to the complete oxidation of chromium ions to hexavalent chromium and the absence of pentavalent chromium in the mesoporous matrix.     

Immobilization of a zirconium complex bearing bis(phenoxyketimine) ligand on MCM-41 for ethylene polymerization

A novel zirconium complex bearing bis(phenoxyketimine) ligand (1) bis((3,5-di-tert-butyl-C₆H₂-2-O)PhCN(2,4-di-fluoro-C₆H₃))ZrCl₂ (2) was prepared and successfully immobilized on a mesoporous molecular sieve MCM-41 in chemical method. Results of slurry polymerization of ethylene with MCM-41-supported catalyst (MC) indicated that the morphologies of polyethylene obtained differed greatly in heptane and toluene. Homogeneous catalyst 2 exhibited a very high initial activity in ethylene polymerization at room temperature resulting in great viscosity of the system. When immobilized on MCM-41, MC showed a smooth yet highly active kinetic behavior. With MAO as the cocatalyst, the effects of Al/Zr molar ratio and polymerization temperature on catalytic activity and properties of polyethylene obtained were investigated. The results showed that polyethylene obtained with MC possessed higher molecular weight (M_n) and broader molecular weight distribution (M_w/M_n) than those formed with its homogeneous counterpart.     

Silica Gel Anchored Chiral Mn(III)Salen Complexes for Enantioselective Epoxidation of Unfunctionalised Olefins

Heterogeneous Mn(III) chiral salen complexes are prepared through covalent attachment of salen ligand on silica gel via chloropropyl spacer and subsequent complexation with manganese. The complexes are well characterized by IR, UV/VIS, TGA and elemental analysis. Epoxidation of unfunctionalised prochiral olefins by Mn(III) chiral salen complexes using iodosobenzene and m-CPBA as the terminal oxidants and NMO as a co-oxidant was achieved with good yields albeit low enantiomeric excess.     

Application of new unsymmetrical chiral Mn(III), Co(II,III) and Ti(IV) salen complexes in enantioselective catalytic reactions

New unsymmetrical chiral salen complexes were synthesized and the efficiency of Mn(III), Ti(IV), Co(II) and Co(III) type catalysts were examined in the enantioselective epoxidation of styrene and α‐methylstyrene, the trimethylsilylcyanation of benzaldehyde, the borohydride reduction of aromatic ketones and asymmetric hydrolysis of epoxides to diols, respectively. A very high level of enantioselectivity was attainable over the unsymmetrical chiral salen complexes prepared mainly from salicylaldehyde and 2‐formyl‐4,6‐di‐tert‐butylphenol derivatives. Enantiomeric excess of the corresponding reaction product obtained using unsymmetrical chiral salen catalysts was generally higher than that over conventional symmetric chiral salen catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mesoporous (Cr)MCM-41 and (Cr)MCM-48 Molecular Sieves: Promising Heterogeneous Catalysts for Liquid Phase Oxidation Reactions

Chromium-containing mesoporous MCM-41 and MCM-48 silicate molecular sieves were synthesized and characterized. Unlike the chromium-containing microporous materials, the mesoporous analogues show significant activity for the chosen (ethylbenzene oxidation) reaction even after several recycling or washing treatments.     

Salen锰催化不对称环氧化烯烃及固载的研究现状

Salen-Mn(Ⅲ)配合物与卟啉铁的结构和性质相似,其在不对称催化反应中具有高对映异构选择性。重点介绍了Salen-Mn(Ⅲ)的配体合成方法、其催化环氧化反应的机理,并对影响催化不对称环氧化反应因素进行了详细阐述。将Salen-Mn(Ⅲ)固载到固体载体上,催化剂分子充分分离,避免形成片μ-oxo-Mn(Ⅵ)二聚体,从而保持催化剂的活性,并易于回收均相催化剂固载化技术的应用,有力地推动了金属Salen-Mn(Ⅲ)配合物应用研究的发展。     

Aerobic photochemical oxidation in mesoporous Ti-MCM-41: epoxidation of alkenes and oxidation of sulfides

Irradiation with visible light of a secondary alcohol, benzhydrol, in the presence of molecular oxygen within a titanium-substituted mesoporous molecular sieve, Ti-MCM-41, led to the formation of the α-hydroperoxoalcohol and then hydrogen peroxide. The peroxide species reacted in situ with alkenes and sulfides and led to the titanium center catalyzed selective formation of epoxides from alkenes and sulfoxides from sulfides. The cascade of reactions represents a new method for the photoactivation of oxygen in the presence of alcohols. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and catalytic activity of new macrocyclic chiral salen complexes

New macrocyclic chiral salen complexes were synthesized and then the efficiency of these fully symmetrical ligands as catalysts was evaluated in the asymmetric epoxidation of olefins and borohydride reduction of ketones. The symmetrical macrocyclic salen complexes exhibited a relatively high enantioselectivity in these reactions.     

Synthesis of a siliceous MCM-41 using C22TMACL template and preparation of heterogenized new chiral salen complexes

Purely siliceous MCM-41 has been prepared under both mild and acidic conditions by a solvent evaporation method using C₁₆TMABr and C₂₂TMACl surfactant as templates. A hydrothermal synthesis was also carried out by utilizing a method of adjusting the gel pH to 10. The mesoporous samples synthesized in ethanol solvent by using this evaporation method showed a fully disordered pore system, but those obtained in the hydrothermal synthesis had highly ordered pores. The chiral salen Mn(III) complexes were immobilized on the siliceous MCM-41 by a new grafting method using 3-aminopropyltrimethylsilane and diformylphenols. These ligands on MCM-41 were stable during the reactions. High enantioselectivities were displayed in the epoxidation of styrene by using these heterogenized salen complexes.     

Surface-modified Improvement in Catalytic Performance of Cr(salen) Complexes Immobilized on MCM-41 in Solvent-Free Selective Oxidation of Benzyl Alcohol

A series of typical methyl regulators were used to finely modify the Cr(salen) complex immobilized on MCM-41. Such immobilized complexes were effective catalysts for solvent-free selective oxidation of benzyl alcohol (BzOH) with 30% hydrogen peroxide (H₂O₂), and they all exhibited much higher catalytic performance than their homogeneous analogue. Simultaneously, the introduction of methyl regulators was found to significantly improve the catalytic performance of immobilized complexes by modifying their surface properties. The optimal BzOH conversion reached 65.0% with 100% selectivity to benzaldehyde (BzH).     

Hydroxylation of phenol by iron(II)-phenanthroline(Phen)/MCM-41 zeolite

MCM-41 mesoporous molecular sieve and iron(II)-Phen/MCM-41 have been prepared and characterized by XRD, IR, NH₃-TPD, BET and UV-Vis. The iron(II)-Phen/MCM-41 molecular sieve + 30% H₂O₂ system is capable of performing hydroxylation of phenol.     

Catalytic combustion of toluene on Cu-Mn/MCM-41 catalysts: Influence of calcination temperature and operating conditions on the catalytic activity

Catalytic combustion of toluene on Cu-Mn/MCM-41 catalyst was performed in tubular flow reactor operated at atmospheric pressure. The effect of catalyst pre-treatment temperatures on the catalytic activity and stability was investigated. Some reaction variables, such as inlet concentration of toluene and oxygen, reaction temperatures and space velocities were varied over wide ranges, and the influence of different reaction conditions on toluene conversion was discussed. It is showed that the catalytic activity was significantly affected by calcination temperatures between 300 and 800 °C, and oxygen concentration, toluene concentration and space velocity are all key experimental factors to optimize the toluene combustion activities. The objective of this study was to investigate catalytic properties of Cu-Mn/MCM-41 catalysts prepared at different calcination temperatures, in order to obtain additional information to prepare an efficient and highly active catalyst at low temperature.     

Active copper species in 1-butene skeletal isomerization: comparison between copper-modified MCM-41 and beta catalysts

The role of copper was studied in the skeletal isomerization of 1-butene over copper-modified mesoporous MCM-41 molecular sieve and Beta zeolite. The Cu–H-MCM-41 and Cu–H-Beta catalysts were synthesized in our laboratory and characterized by XRD, nitrogen adsorption, X-ray fluorescence, FTIR of adsorbed pyridine and direct current plasma atomic emission spectrometry. The oxidation state of copper after oxidation and reduction in Cu–H-MCM-41 was evaluated by FTIR with probe molecules. Copper ion-exchanged and the proton forms of MCM-41 and Beta catalysts were tested towards 1-butene skeletal isomerization by varying the weight hourly space velocity and temperature. Quantum chemical calculations at the B3LYP/6-31 + G^** level were performed in order to understand the role of copper at the molecular level.

Copper in Cu–H-MCM-41 pretreated in synthetic air was mostly in the form of Cu²⁺ but reduced during the catalytic experiment to the metallic form Cu⁰ via Cu⁺. Even if the copper exchange decreased the amount of Brønsted acid sites, Cu–H-MCM-41 pretreated in synthetic air was more active than H-MCM-41 towards 1-butene skeletal isomerization. The enhanced catalytic activity is due to copper Cu⁺, which was formed during the reaction. Introduction of copper into H-Beta, however, did not have any effect at all on the performance of the catalyst. The probable reason for this is the high initial activity of copper-modified H-Beta causing a very fast reduction of copper to the inactive metallic form Cu⁰.     

Epoxidation of Olefins Catalyzed by Mn(II) Salen Complex Anchored on PAMAM–SiO2 Dendrimer

New dendritic catalysts have been prepared by the immobilization of a Mn(II) salen complex on a polyamidoamine dendrimer propagated on the surface of silica. These have been applied in the catalytic epoxidation of olefins. Although the increase of the amount of Mn loading is found to be limited on high-generation dendrimers, the Mn(II) salen complex anchored on the fourth-generation dendrimer shows much higher catalytic activity toward the epoxidation of styrene than that anchored on lower generations. These results suggest that the length of the dendritic backbone chain plays an important role in increasing the accessibility between the catalytic active sites of the immobilized Mn(II) salen complex and the reactant molecules, resulting in the enhancement of the catalytic activity of the Mn(II) salen complex anchored on the fourth-generation dendrimer.