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.     

Tethering of Cu(II) Schiff base metal complex on mesoporous material MCM-41: catalyst for Ullmann-type coupling reactions

The siloxane-functioned Cu(II) complex derived from 3-aminopropyltrimethoxysilane, terephthaldehyde and 2-aminophenol was anchored on hexagonal mesoporous silica MCM-41. The MCM-41 and its Schiff base MCM-41 complex was characterized by FTIR, small-angle X-ray diffraction, SEM-EDX, N₂ adsorption and desorption analysis and TGA. The synthesized Cu-Schiff base MCM-41 catalyst has been successfully applied as a catalyst for Ullmann-type coupling reaction of the aryl halides with aryl halides, phenols, amines and N-heterocyclic amines. In the coupling reaction the yields of the products were good and the catalyst was recovered by simple filtration method and can be reused.     

Schiff base complex of Cu immobilized on MCM-41 as reusable catalyst for efficient oxidative coupling of thiols and oxidation of sulfides using hydrogen peroxide

Schiff base complex of copper-functionalized MCM-41 (Cu-complex@MCM-41) was synthesized and used as an efficient and novel heterogeneous catalyst for the oxidative coupling of thiols into corresponding disulfides and oxidation of sulfides to sulfoxides using hydrogen peroxide (H₂O₂) as the oxidant. An aliphatic and aromatic series of sulfides and thiols including various functional groups were successfully converted into corresponding products. The all products were obtained in good to excellent yields. The mesoporous catalyst is characterized by FT-IR spectroscopy, BET, XRD, SEM, EDS and TGA. Recovery of the catalyst is easily achieved by simple filtration and reused for several consecutive runs without significant loss of its catalytic efficiency.     

The oxidation of sulfide to sulfoxide on Ti-complex/MCM-41 catalyst

The heterogeneous Kagan-type catalyst was prepared by an in situ method using MCM-41 as support. The influence of the incorporation process on the structure of MCM-41 was studied using XRD, FT-IR, UV-vis, ²⁹Si-MAS-NMR and N₂ adsorption–desorption. The obtained materials showed a definite catalytic activity on the oxidation of sulfide to sulfoxide in the medium containing dichloromethane (solvent) and H₂O₂ or TBHP (oxidant).     

Synthesis,characterization and sulfide oxidation activity of vanadyl Schiff base complexes anchored on MCM-41

Vanadyl Schiff base complexes covalently attached on the surface of MCM-41 have been synthesized by anchoring Schiff base and subsequent reaction with VO(acac)₂. XRD, nitrogen adsorption and desorption, UV-visible spectroscopy and FT-IR show that vanadyl Schiff base complexes were successfully anchored on the surface of MCM-41 and the mesopore ordering decreased after the anchoring. The so-prepared heterogeneous catalysts have showed high activity for sulfide oxidation.     

Zr (IV)-ninhydrin supported MCM-41 and MCM-48 as novel nanoreactor catalysts for the oxidation of sulfides to sulfoxides and thiols to disulfides

Modification of MCM-41 and MCM-48 mesoporous materials with bonded aminosilane species, Schiff base preparation by ninhydrin and finally complexation with zirconium, has attracted much attention in order to design catalyst with advanced applications in the oxidation of sulfides to sulfoxides and thiols to disulfides in the presence of hydrogen peroxide. In all oxidation of sulfides to sulfoxids 0.4 mL H₂O₂ used as oxidant in the presence of Zr(IV)-ninhydrin supported MCM-41 (0.01 g) or Zr(IV)-ninhydrin supported MCM-48 (0.005 g) at room temperature and solvent-free condition. Also the best conditions for oxidation of thiols to disulfides with 0.4 mL H₂O₂ were 0.005 g Zr(IV)-ninhydrin supported MCM-41 or Zr(IV)-ninhydrin supported MCM-48 at room temperature and in ethanol. These catalysts are characterized by SEM, XRD, TGA, FT-IR, EDS, ICP and BET analysis. Also the Turn over frequency (TOF) and Turn over number (TON) of catalysts are calculated. Obtained results by these heterogeneous catalysts revealed several advantages including short reaction times, simple workup, easy isolation and reusability.     

Oxovanadium (IV) Schiff base complex immobilized on CPS microspheres as heterogeneous catalyst for aerobic selective oxidation of ethyl benzene to acetophenone

In this work, chloromethylated crosslinked polystyrene microspheres (CMCPS microspheres) were used as starting carrier, and a new immobilized bidentate Schiff base oxovanadium (IV) complex catalyst was prepared. The chloromethyl groups of CMCPS microspheres were first transformed into aminomethyl groups via Delepine reaction with hexamethylene tetramine (HMTA) as reagent, obtaining aminomethylated (AM) microspheres AMCPS. And then the Schiff base reaction between the primary amino group of AMCPS microspheres and salicylaldehyde (SA) was allowed to be conducted, resulting in Schiff base-type resin microspheres, SAAM-CPS, on which bidentate Schiff base ligand SAAM were chemically anchored. Subsequently, the coordination reaction between the ligand SAAM of SAAM-CPS microspheres and vanadyl sulfate (VOSO₄) was carried out, obtaining a new immobilized bidentate Schiff base-type oxovanadium (IV) complex, CPS-[VO(SAAM)₂] microspheres, namely a new heterogeneous oxovanadium (IV) complex catalyst was prepared. On the basis of fully characterizing the microspheres CPS-[VO(SAAM)₂], they were used in the catalytic oxidation of ethyl benzene with molecular oxygen. The experimental results show that in the oxidation reaction of ethylbenzene with molecular oxygen as oxidant, the heterogeneous oxovanadium (IV) complex catalyst, CPS-[VO(SAAM)₂], has high catalytic activity and excellent catalytic selectivity. Under the mild conditions such as at ordinary pressure of dioxygen and at a relatively low temperature of 110 °C, ethyl benzene can be transformed to acetophenone as a single product with a yield of 43%. It was found that the reaction temperature and the used amount of the solid catalyst effect on the oxidation reaction greatly. The catalyst CPS-[VO(SAAM)₂] has excellent recycle and reuse property.     

A Highly Efficient Catalyst Au/MCM-41 for Selective Oxidation Cyclohexane Using Oxygen

The liquid-phase highly efficient selective oxidation cyclohexane to cyclohexanol and cyclohexanone over Au/MCM-41 catalyst was carried out in a solvent-free system, which oxygen as the only oxidant and the reaction conditions are very moderate. The Au/MCM-41 was characterized by XRD, N₂adsorption/desorption, UV-Vis, XPS, and ICP-AES.     

Highly selective oxidation of alcohols catalyzed by Cu(II)-Schiff base-SBA-15 with hydrogen peroxide in water

An efficient catalyst for selective oxidation of alcohols was prepared by grafting the Cu(II) Schiff base complex onto the channels of mesoporous silica material SBA-15. The characterizations illustrated that the functionalized SBA-15 maintained the primary hexagonally ordered mesoporous structure, and the Cu(II) Schiff base complexes were bonded inside the mesoporous channels of SBA-15. The selective oxidation of benzyl alcohol was carried out in water phase with hydrogen peroxide. The C₆H₅CH₂OH conversion could reach 98.5 % with 100 % of the selectivity to C₆H₅CHO under the optimum conditions. The catalyst could also react well on the selective oxidation of other primary alcohols.     

Synthesis, Characterization of Ag/MCM-41 and the Catalytic Performance for Liquid-phase Oxidation of Cyclohexane

Nano-scale silver supported mesoporous molecular sieve Ag/MCM-41 was directly prepared by one-pot synthesis method. The prepared sample was characterized by XRD, TEM, and N₂ sorption. The results showed that the sample of Ag/MCM-41 had no appreciable incorporation of silver into the mesoporous matrix of MCM-41 with good crystallinity, and silver nanoparticles were dispersed inside or outside of the channels in the mesoporous host. The catalytic performance of the sample for the cyclohexane liquid-phase oxidation into cyclohexanone and cyclohexanol by oxygen in the absence of solvents without inducing agents was investigated. The 83.4% selectivity to cyclohexanol and cyclohexanone at 10.7% conversion of cyclohexane was obtained over Ag/MCM-41 catalyst at 428 K for 3 h. The turn over numbers (TONs) of Ag/MCM-41 was up to 2946. The catalytic activity of Ag/MCM-41 was also compared with Ag/TS-1 as well as Ag/Al₂O₃. The results indicated that Ag/MCM-41 showed superior activity to both Ag/TS-1 and Ag/Al₂O₃. A calcined Ag/MCM-41 was found to be an efficient catalyst for the cyclohexane oxidation into cyclohexanol and cyclohexanone using oxygen as oxidant.     

Molybdenum Schiff Base Complex Covalently Anchored to Silica-Coated Cobalt Ferrite Nanoparticles as a Novel Heterogeneous Catalyst for the Oxidation of Alkenes

Abstract  

Silica-coated cobalt ferrite nanoparticles were prepared and functionalized with Schiff base groups to yield immobilized bidentate ligands. The functionalized magnetic nanoparticles were then treated with Mo (O₂)₂(acac)₂, resulting in the novel immobilized molybdenum Schiff base catalyst. The as-prepared catalyst was characterized by X-ray powder diffraction, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, and inductively coupled plasma atomic emission spectroscopy. The immobilized molybdenum complex was shown to be an efficient heterogeneous catalyst for the oxidation of various alkenes using t-BuOOH as oxidant. This catalyst, which is easily recovered by simple magnetic decantation, could be reused several times without significant degradation in catalytic activity.     

MCM-41-supported NNO type Schiff base complexes: a highly selective heterogeneous nanocatalyst for esterification,Diels–Alder and aldol condensation

Solid catalysts have been synthesized by anchoring transition metal complexes into organically modified MCM-41. First, the surface of Si-MCM-41 was modified with 3-aminopropyl-triethoxysilane (3-APTES), the imine group of which upon condensation with DFP (4-methyl-2,6-diformylphenol) affords a N₂O-type Schiff base moiety in the mesoporous matrix. The Schiff base moieties were used to anchor Ni (II) and Cu (II) ions. The prepared catalyst have been characterized by DRS (Diffuse Reflectance Spectroscopy), FTIR (Fourier transform infrared) spectroscopy, small-angle X-ray diffraction (SAX), FESEM (Field Emission Scanning Electron Microscope), EDX (Energy-dispersive X-ray spectroscopy) and nitrogen sorption studies. The decrease of crystallinity in the multistep synthesis procedure, as evidenced by SAX (Small-angle X-ray) measurements, was observed. The prepared materials proved to be efficient catalysts for organic transformations such as esterification, Diels–Alder and Aldol condensation at ambient conditions. The immobilized complex does not leach or decompose during the catalytic reactions, showing practical advantages over the free metal complex.     

Synthesis and Characterization of Copper(II)–Cysteine/SiO2–Al2O3 as an Efficient and Reusable Heterogeneous Catalyst for the Oxidation of Aromatic Alcohols

In the present study, heterogeneous copper(II)–cysteine/SiO₂–Al₂O₃ catalyst was successfully prepared by a simple adsorption method. The physical and chemical properties of Cu(II)–cysteine/SiO₂–Al₂O₃ were investigated by X-ray diffraction, thermal gravimetric analyzer, FT–IR spectroscopy, Brunauer–Emmett–Teller, UV–Vis spectroscopy, scanning electron microscopy and atomic absorption spectrometer. The obtained composite was effectively employed as catalyst for selective oxidation of various aromatic alcohols to corresponding aldehydes in high yields using hydrogen peroxide as an oxidant under mild condition. The catalyst can be recycled over five times without significant loss of activity.     

Preparation of MCM-41 Supported Salen Vanadium Complex and its Catalysis for the Oxidation of Cyclohexane with H<Subscript>2</Subscript>O<Subscript>2</Subscript> as an Oxidant

A secondary amino group modified MCM-41 (mobile crystalline material number 41) was synthesized and used as a support for the immobilization of a salen oxovanadium complex via a multi-grafting method. The immobilized complex was characterized by UV–Vis spectroscopy, X-ray diffraction (XRD), N₂ adsorption and ICP analysis techniques. The immobilized complex was found to be an effective catalyst for oxidation of cyclohexane using H₂O₂ as an oxidant under mild conditions. A conversion of 45.5% of cyclohexane was obtained with a selectivity of 100% of the cyclohexanone/cyclohexanol mixture when the reaction was run at 60 °C for 12 h in acetonitrile. Decomposition of the complex, which leads to the deactivation of the catalyst, is observed and a decomposition mechanism is discussed.     

Functionalization of oxo-vanadium(IV) acetylacetonate over modified MCM-41: an efficient reusable catalyst for epoxidation reaction

A new hybrid heterogeneous catalytic system has been developed by post synthesis grafting method. 3-aminopropyltriethoxysilane (3-APTES) has been first anchored over mesoporous silica materials MCM-41. Upon reaction with oxo-vanadium(IV) acetylacetonate amine groups of 3-APTES afford vanadium(IV) active centers in the mesoporous matrix. The prepared hybrid material has been characterized by UV–vis, infrared (IR) spectroscopic analysis, small-angle X-ray diffraction and N₂ sorption studies and employed in epoxidation reactions as a catalyst. The catalyst showed excellent catalytic activity towards epoxidation reaction with various olefinic compounds using tert-BuOOH as oxidant under mild reaction condition. The effect of different solvents on epoxidation reaction has also been studied.     

Mo incorporation in MCM-41 type zeolite

Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N₂-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H₂O₂ as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41. This revised version was published online in July 2006 with corrections to the Cover Date.     

Efficient Allylic Oxidation of Olefins Catalyzed by Polymer Supported Metal Schiff Base Complexes with Peroxides

Three homogeneous Cu(II), Co(II) and Ni(II) complexes of a Schiff base ligand and their heterogeneous complexes supported on poly(4-aminostyrene) were prepared and characterized by using elemental analysis, fourier transform infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, thermogravimetric analysis and scanning electron microscopy. The catalytic performance of both homogeneous and heterogeneous complexes was evaluated in the liquid phase oxidation of cyclohexene, styrene and trans-stilbene in acetonitrile with tert-butylhydroperoxide or hydrogen peroxide as the oxidant. All types of catalyst were active in oxidation; and, the complexes produce allylic oxidation products in all cases. Immobilized complexes are slightly more active than their homogeneous complexes. The polymer-supported Cu(II) complex shows a higher catalytic activity than the other metal species. The activities of the immobilized catalysts remained nearly the same after five cycles, suggesting the true heterogeneous nature of the catalyst.     

An efficient oxidation of cyclohexane over Au@TiO2/MCM-41 catalyst prepared by photocatalytic reduction method using molecular oxygen as oxidant

Cyclohexane oxidation using molecular oxygen as oxidant is one of the most challenge subjects. A novel photocatalytic reduction method to prepare Gold nanoparticles Au@TiO₂/MCM-41 was proposed. The prepared samples were characterized by XRD, N₂ adsorption isotherm, FT-IR, TEM and EDS. The results showed that gold nanoparticles were well-dispersed on TiO₂/MCM-41, and TiO₂ was dispersed on the surface of the support and the gold existed as Au⁰. Newly-developed catalyst was promising for the cyclohexane oxidation, achieving a turnover frequency (TOF) as high as 29,145 h^− 1 with 9.87% conversion of cyclohexane.     

Catalytic study of MCM-41 immobilized RhCl3 for the hydroformylation of styrene

RhCl₃ was chemically immobilized on mesoporous silicate MCM-41 functionalized by amine or phosphorus organosilane to form heterogeneous catalysts: RhCl₃/MCM-41(NH₂) and RhCl₃/MCM-41(PPh₂). XRD and N₂ adsorption–desorption studies illustrated that the functionalized MCM-41 maintained the mesoporous structural ordering, but exhibited reduced pore sizes, total pore volumes and BET surface areas. XPS characterization indicated that chemical interaction between rhodium species of RhCl₃ and the surface ligands occurred, and rhodium (III) species were reduced to lower oxidation states. RhCl₃/MCM-41(NH₂) was tested to be stable for recycling, however a significant rhodium leakage was observed for RhCl₃/MCM-41(PPh₂). The catalytic system formed of the prepared RhCl₃/MCM-41(NH₂) catalyst and additional PPh₃ (PPh₃/Rh = 2.5) showed very good catalytic activity and high selectivity toward the branched aldehydes in the hydroformylation of styrene.     

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.