Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene

New tetradentate chelates of bis-Schiff bases were synthesized and then these chiral salen ligands were immobilized over mesoporous MCM-41 by using the ion-exchange method. The efficiency of the chiral catalyst was examined in the asymmetric epoxidation of styrene. Chiral Mn(salen) complexes immobilized onto mesoporous MCM-41 were stable during the reaction without any leaching and exhibited relatively high enantioselectivity for epoxidation as compared with homogeneous complexes. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

The synthesis of new chiral salen complexes immobilized on MCM‐41 by grafting and their catalytic activity in the asymmetric borohydride reduction of ketones

The new chiral salen complexes were synthesized and supported on mesoporous MCM‐41 through the condensation of 3‐aminopropyltrimethoxysilane and 2,6‐diformyl‐4‐tert‐butylphenol by the multi‐grafting method. The immobilized optically active Co(II) salen complexes showed a very high enantioselectivity in the asymmetric borohydride reduction of aromatic ketones. The chiral salen Co(II) complexes immobilized over MCM‐41 were stable during the reaction and exhibited a relatively high enantioselectivity for the reduction of ketones as compared with the homogeneous salen catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Synthesis of polymeric salen complexes and application in the enantioselective hydrolytic kinetic resolution of epoxides as catalysts

The polymeric (salen) Co(III) catalysts containing various counter anions have been synthesized, and the asymmetric catalytic activities of these newly synthesized polymer-type salen complexes were investigated in the HKR of terminal epoxides. The polymeric chiral salen Co(III) complexes catalyze the hydrolysis of epichlorohydrine, 1,2-epoxybutane, 1,2-epoxyhexane and epoxystyrene with very high enantioselectivities under mild conditions. The catalysts could be recovered and reused several times without further treatment after reaction, showing no loss of activity and enantioselectivity.     

Mesoporous Silica Supported Unsymmetric Chiral Mn(III) Salen Complex: Synthesis,Characterization and Effect of Pore Size on Catalytic Performance

An unsymmetric chiral Mn(III) salen complex was immobilized onto a series of MCM-41 and MCM-48 mesoporous materials with different pore sizes. The as-synthesized catalysts were characterized by XRD, FT-IR, DR UV-Vis, N₂ sorption and XPS. The results indicated that chiral Mn(III) salen complex was immobilized into the nanopores of supports and the long-range mesoporous ordering of parent supports was maintained after the immobilization. The heterogeneous catalysts were evaluated in the asymmetric epoxidation of styrene, indene, and 1-phenylcyclohexene, and the effect of 3-mercaptopropyltrimethoxysilane dosage and fine-tuning of pore size on the catalytic performance was studied. It was found that the activity and enantioselectivity were closely correlated with the pore sizes of heterogeneous catalysts. The larger pore sizes of supports could lead to higher conversions and ee values.     

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.     

Enantioselectivities of Chiral Ti(IV) Salen Complexes Immobilized on MCM-41 in Asymmetric Trimethylsilylcyanation of Benzaldehyde

A new heterogeneous system for catalytic trimethylsilylcyanation of benzaldehyde has been developed by immobilizing Ti(IV) salen onto ordered mesoporous silica (MCM-41). The immobilization was performed according to different methods: (i) direct condensation of silanol on the silica surface with Ti(IV) salen and (ii) multigrafting of salicylaldehyde derivatives and diaminocyclohexane using 3-mercaptopropyl-functionalized MCM-41 as a starting material. The heterogenized salen catalysts showed a high enantioselectivity for the addition of trimethylsilyl cyanide to benzaldehyde.     

Asymmetric Epoxidation of Styrene on the Heterogenized Chiral Salen Complexes Prepared from Organo-Functionalized Mesoporous Materials

Organosilane-modified mesoporous materials have been prepared under mild and acidic conditions by a solvent evaporation method using C₁₆TMABr surfactant as a template. The mesoporous samples synthesized in ethanol solvent by using this evaporation method showed a fully disordered pore system, but those obtained under hydrothermal conditions had highly ordered pores. The chiral salen Mn(III) complexes were immobilized on these organosilane-functionalized mesoporous silicas by a grafting method. The catalysts used in the asymmetric epoxidation of styrene and cis-stilbene and the effect of different mesoporous structures on the reactivity was investigated. Similar enantioselectivities were observed by using these heterogenized salen complexes as compared with reaction under homogeneous conditions.     

Covalently bonding assembly and photophysical properties of luminescent molecular hybrids Eu–TTA–Si and Eu–TTASi–MCM-41 by modified thenoyltrifluoroacetone

In the context, the two novel kinds of hybrid materials, TTA–Si directly chemically bonded molecular hybrids and the corresponding MCM-41 host assembling hybrids were prepared. The organic–inorganic mesoporous luminescent materials were synthesized by linking Eu³⁺ complexes to the functionalized ordered mesoporous MCM-41 with modified thenoyltrifluoroacetone (TTA–Si) by co-condensation of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template. Thenoyltrifluoroacetone (TTA) was grafted with coupling agent 3-(triethoxysilyl)-propyl isocyanate and the as-derived functional bridge molecule (denoted as TTA–Si) was introduced into inorganic polymeric host MCM-41 through covalent bonds, resulting in the molecular hybrid material. The luminescence properties of these resulting materials were characterized in detail, and the results reveal that they all have high surface area, uniformity in the mesostructure and crystallinity. The efficient intramolecular energy transfer in mesoporous material Eu–TTASi–MCM-41 mainly occurs between the modified ligand TTA–Si and the central Eu³⁺ ion. In addition, the constructed covalently bonded hybrids present the longer luminescent lifetimes than common Eu(III) β-diketones complexes for improvement of stability. Especially the mesoporous luminescent material Eu–TTASi–MCM-41possesses high luminescence quantum efficiency.     

Design and synthesis of near-IR luminescent mesoporous materials covalently linked with tris(8-hydroxyquinolinate)lanthanide(III) complexes

By using the bifunctional ligand, 8-hydroxyquinoline-functionalized organosilane (Q-Si), the new mesoporous material Q–MCM-41 covalently bonded with 8-hydroxyquinoline was synthesized. Through the ligand exchange reaction, the new near-infrared (NIR) luminescent mesoporous LnQ₃–MCM-41 (Ln = Er, Nd, Yb) materials were prepared by linking the lanthanide quinolinate complexes to the ordered mesoporous Q–MCM-41 material. The LnQ₃–MCM-41 materials were characterized by powder X-ray diffraction and N₂ adsorption/desorption, and they all show the characteristic mesoporous structure of MCM-41 with highly uniform pore size distributions. Fluorescence spectra of these LnQ₃–MCM-41 materials were recorded and the corresponding luminescence decay analyses were measured. After ligand-mediated excitation, all the emission spectra of the LnQ₃–MCM-41 materials show the characteristic NIR-luminescence of the corresponding lanthanide ions via the intramolecular energy transfer from the ligands to the lanthanide ions. The good luminescent performances enable these NIR-luminescent mesoporous materials to have potential applications in optical amplification (operating at 1.3 or 1.5 μm) and laser systems, etc.     

Methanol oxidation on LaCo mixed oxide supported onto MCM-41 molecular sieve

Lanthanum cobaltate LaCoO_x supported onto MCM-41 mesoporous molecular sieve was prepared by in-situ oxidative decomposition of mixed LaCo citrate complexes inside the mesopores of this support. The prepared materials were characterized by EDX, EPR and UV-Vis DRS techniques as well as by N₂-BET measurements. The nanosized LaCoO_x particles within the mesopores of MCM-41 matrix contains cobalt atoms in lower than Co(III) average oxidation state. Also, the supported cobaltate does not form short-range order species of LaCoO₃ but presents as the highly disordered, oxygen deficient Co oxide nanophase. Catalytic activity in MeOH oxidation was tested using both conventional fixed-bed flow system and “operando” mode of DRIFT technique. The very high activity of MCM-41-supported cobaltate is not only due to highly dispersed LaCoO₃ phase but also because of rather low oxidation state of Co.     

MCM-41介孔材料的合成条件和特性对吸附镉离子的影响

以气相氧化硅为硅源,十六烷基三甲基溴化铵(cetyl trimethyl ammonium bromide,CTAB)为模板剂,分别在碱性[氢氧化钠(NaOH),四乙基氢氧化铵,tetraethyl ammonium hydroxide,(C2Hs)4NOH(TEAOH)]和酸性介质条件[盐酸(HCl)]T水热合成了MCM-41有序介孔材料MCM-41-N,MCM-41-T和MCM-41-H.用X射线衍射、氮气吸附-脱附等手段对比分析了合成的3种MCM-41介孔材料的物相、比表面积、孔径、孔体积等,发现酸性介质中合成的介孔材料的孔径最大.在此基础上,利用MCM-41介孔材料对比研究了处理含镉离子(Cd2 )废水的效果和机理,确定了不同介孔材料用量、不同初始pH值条件下MCM-41介孔材料对水中Cd2 的吸附率和吸附量.结果表明:介孔材料用量相同时,溶液pH值的增大有利于提高3种MCM-41介孔材料对水中Cd2 的处理效果.在pH值从7.0到8.0的过程中,其吸附率有1个突变,MCM-41-T的Cd2 吸附率从35.65%提高到62.15%;MCM-41-N的从38.80%提高到69.40%;MCM-41-H的从50.22%提高到73.47%.孔径最大的MCM-41-H对Cd2 的吸附效果最佳,最大吸附率为89.56%,最大吸附容量为8.57 mg/g.吸附溶液pH值的大小和介孔材料的孔径尺寸是决定吸附量大小的关键因素,因此,重点应通过优化合成工艺提高介孔材料的孔径.     

Facile synthesis of sulfo-functionalized mesoporous silica with strong acidity by temperature-controlled calcination

The facile synthesis of sulfo-functionalized mesoporous silica (MCM-41) by a one-step process of surfactant removal and thiol oxidation technique through a temperature-controlled calcination of a precursor is presented. Thiol containing mesoporous silica is synthesized as a precursor by hydrolysis and co-condensation of tetramethoxysilane (TMOS) and mercaptopropyl trimethoxysilane (MPTMS). The samples thus prepared are shown to preserve the ordered two-dimensional hexagonal structure and pore characteristics of MCM-41, while functionalizing the material with sulfo groups which was oxidized from thiol groups providing strong acidity. The acidity of the material is demonstrated by high ammonia uptakes and low differential adsorption energy of ammonia.     

Immobilization of Ru(II)(salen)(PPh3)2 on Mesoporous MCM-41/SBA-15: Characterization and Catalytic Applications

Ru(II)(salen)(PPh₃)₂ immobilized on MCM-41 and SBA-15 modified with aminopropyl groups as linkers has been synthesized and characterized by elemental analysis, TEM, FTIR, BET, and TGA. Elemental analysis shows that the grafted samples contain 0.7–0.8 wt.% Ru. The retaining of long range ordering of the mesoporous MCM-41 and SBA-15 supporting materials after grafting is evident from TEM and N₂ adsorption/desorption measurements. FTIR and TGA spectra show the formation of metal salen complexes with the amino groups acting as connectors to the SiO₂ surface. Both grafted materials were successfully applied as catalysts for the olefination of various aldehydes with very good yields and high E-selectivity. The catalyst materials are recyclable for several catalytic runs.     

Synthesis and investigation of anchored copper (II) complexes within MCM-41 as selective catalysts for epoxidation of olefins

In the present study, preparation, characterization and catalytic activity of encapsulated copper (II) complexes within MCM-41 were investigated. The mesoporous molecular sieve MCM-41 was synthesized and grafted with 3-(trimethoxysilyl)-1-propanethiol to give a thiol modified material (MCM-41-S). The prepared material successively was reacted with acrylic acid and acrylonitrile to give AA-MCM-41 and AN-MCM-41, respectively. Using hexamethyldisilazane and copper (II) chloride, copper (II) complexes in the cavities of MCM-41 (Cu-AA-MCM-41 and Cu-AN-MCM-41) were prepared. The presence of copper (II) complex on the surfaces of host matrix and the structure of prepared catalyst is investigated by FT-IR, inductively coupled plasma-optical emission spectroscopy (ICP-OES), powder X-ray diffraction (XRD) and BET nitrogen adsorption–desorption methods. The catalytic activities of the catalysts were studied in epoxidation of olefins. The results showed that activities of the prepared catalysts (Cu-AA-MCM-41 and Cu-AN-MCM-41) and their selectivity to corresponding epoxides were more than those of MCM-41. In addition, the synthesized heterogeneous catalysts were truly reusable.     

Kinetic resolution of terminal epoxides with phenols promoted by heterometallic Co–Al and Co–Ga salen complexes

The binuclear chiral (salen) Co complexes bearing Lewis acid salt (Al and Ga) and 4-nitrobenzene sulfonic acid (NBS) catalyze the enantioselective ring opening of terminal epoxides with phenol derivatives. The easily prepared complexes exhibited very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of terminal epoxides with phenol and consequently provide enantiomerically enriched corresponding α-aryloxy alcohols (up to >99% ee). The two unit of salen complexes combined by Lewis acid exhibited co-operative catalysis during the ring opening reaction.     

改性中孔分子筛MCM-41催化合成丙酸香叶酯

用H2SO4对中孔分子筛MCM（mobile crystalline material）-41进行改性,得到SO42–修饰的中孔分子筛SO42–/MCM-41。通过X射线衍射、红外光谱、NH3程序升温脱附和N2吸附–脱附等方法对所合成样品进行表征。用SO42–/MCM-41催化合成丙酸香叶酯,考察了催化剂处理方法、催化剂用量、催化剂再生对香叶醇酯化反应结果的影响,并比较了H2SO4、MCM-41和SO42–/MCM-41这3种催化剂对合成丙酸香叶酯的催化性能。结果表明：用浓度为0.50mol/L的硫酸浸泡MCM-41中孔分子筛1h,再于450℃焙烧3.0h,能得到良好长程有序性和结晶度的中孔分子筛SO42–/MCM-41,用其催化合成丙酸香叶酯,香叶醇的转化率最高可达88.82%,丙酸香叶酯的选择性为85.20%;H2SO4改性对MCM-41中孔分子筛结构影响不明显,但可提高其酸性。     

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.     

Bidentate salen Cu(II) complex functionalized on mesoporous MCM-41 as novel nano catalyst for the oxidative coupling of thiols into disulfides using urea hydrogen peroxide (UHP)

Functionalized Copper(II) complex into nano dimensional mesoreactor was successfully prepared. The Copper(II) complex with N–O donor Schiff base ligand was readily trapped into mesoporous silica MCM-41 through the post grafting method. N–O Chelating Schiff-base-MCM-41 has been derived from 5-bromo-salicylaldehyde and 3-aminopropyltriethoxysilane which was functionalized on MCM-41 via silicon alkoxide route. This compound was characterized by FT-IR, TGA, small angle X-ray diffraction patterns, ICP/MS analysis and N₂ sorption–desorption analysis. The catalytic property of Cu–salen–MCM-41 was considered for the preparation of disulfides using urea hydrogen peroxide as oxidant. The reaction progress is simple and proceeds under mild and heterogeneous conditions in acetonitrile at the ambient of temperature. The corresponding disulfides have been achieved with high purity and good to excellent yields; also, no over oxidation to sulfoxide or sulfone was observed in all cases. The catalyst can be recovered and reused several times without significant loss of stability and activity.