Molybdenum containing surface complex for olefin epoxidation

Silica-supported molybdenum surface complexes were prepared by the reaction between (N=) Mo(OtBu)(3) and silica via displacement of the tert-butoxy ligands for siloxyls from the silica surface. The structure of the surface molybdenum complexes was well defined by in-situ FT-IR, elemental analysis, H-1 NMR and C-13 CP/MAS NMR techniques. The surface complexes could undergo alcoholysis reaction with CD3OD and CH3OH in the same way as free (N =) Mo(OtBu)(3) and they show high catalytic activity and selectivity in olefin epoxidation. Initial rates up to 24.9 mmol epoxide (mmol Mo)(-1) min(-1) were achieved in the epoxidation of cyclohexene using TBHP as oxidant.

Synthesis and spectroscopic study of mesoporous aluminum methylphosphonate foam templated by dibutyl methylphosphonate

New types of templates and novel interactive mechanisms between template and framework are very important for creating porous materials. In this work, by using neutral dibutyl methylphosphonate as a template, an inorganic-organic hybrid mesoporous material, aluminum methylphosphonate, was prepared. The as-synthesized material was studied by P-31 magnetic angle spinning nuclear magnetic resonance (MAS NMR), Al-27 MAS NMR, C-13 CP/MAS, FT-IR spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), and transmission electron microscopy. After thermal treatment at 673 K and 10 mmHg for 2 h, hybrid mesoporous foam was obtained. The transformation process was investigated by FT-IR. TG-DTA results indicate that the methyl group bonded to the framework keeps intact up to 792 K under air and 823 K under nitrogen. The characterization results from nitrogen gas adsorption-desorption measurements show that the BET surface area and the Barrett-Joyner-Halenda desorption cumulative pore volume of the foam are 90 m(2) g(-1) and 0.32 cm(3) g(-1) respectively. (C) 2003 Elsevier Inc. All rights reserved.

Structure of an unexpected trimer from the reaction of ageratochromene II with aluminum chloride

A new trimer from the reaction of ageratochromene [1] (6,7-dimethoxy-2,2-dimethyl-1-benzopyran) with anhydrous aluminum chloride was shown to be 3,4-dihydro-6,7-dimethoxy-2,2-dimethyl-3-(6',7'-dimethoxy-2',2'-di-methyl-2H-1-benzopyran-4'-yl)-4-(3" 4"-dihydro-6", 7"-dimethoxy-2",2"-dimethyl-2H-1-benzopyran-3"-yl)-2H-1-benzopyran. Its structure was confirmed by NMR (H-1, C-13, DEPT-135. COSY, HMBC, HSQC, TOCSY and NOESY), IR, mass spectra and elemental analysis. Copyright (C) 2002 John Wiley Sons, Ltd.

Calibration of a solid-state copper ion-selective electrode in cupric ion buffers containing chloride

It is shown that near-Nernstian calibration slopes can be obtained with a Cu1.8Se electrode in a range of cupric ion buffers in spite of a high chloride content. Best results are obtained with the ligands ethylenediamine, glycine and histidine. The onset of cupric ion toxicity towards marine organisms falls within the pCu calibration range obtained with glycine, and the Cu1.8Se electrode could, therefore, be useful for monitoring cupric ion activity in bioassays in sea-water media.

The Synthesis and Characterization of a Novel (E,E)-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel (E,E)-dioxime, 5,6:17,18-dibenzo-11,12-(4-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) (H2L), has been synthesized from reaction of (E,E)-dichloroglyoxime (1) with 2,3:14,15-dibenzo 8,9-(4-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane (2). The mononuclear Co(III) complex (4) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex (5) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes (6) and (7) were prepared by reaction of (5) with NiCl2·6H2O and CdCl2·H2O, respectively. In addition, the homotrinuclear Cu(II) complex (8), has also been prepared by the reaction of this dioxime with CuCl2·H2O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1H- and 13C-NMR, IR, and mass spectral data.

Two novel molybdenum complexes containing [Mo2O2S2](2+) fragment: synthesis, crystal structures and catalytic studies

Mo2O2S2(HGly)(GlY)(2) 1 and K-6[Mo2O2S2(nta)(2)][Mo2O2S2(ntaH)(2)]center dot 4H(2)O 2 were synthesized by the reactions of (NH4)(2)MoS4 and amino acids L (L = glycine, nitrilotriacetic acid) in ethanol-water medium at ambient temperature. The two complexes were characterized by elemental analysis, infrared spectra, UV-visible spectra, TG-DTA and XPS.

Dynamic mechanical properties of gel polymer electrolytes containing ionic liquid

The copolymer of acrylonitrile (AN), methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) is synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). The dynamic mechanical properties of the resulting gel polymer electrolytes containing ionic liquid are measured.

Microstructure and mechanical properties of Mg-12.3Zn-5.8Y-1.4Al alloy

Microstructure and mechanical properties of as-cast and heat-treated Mg-12.3Zn-5.8Y-1.4Al (ZYA1261) alloy were investigated. The phase compositions of the as-cast alloy are alpha-Mg, Mg3YZn6 (I-phase), Mg(3)y(2)Zn(3) (W-phase), Mg12YZn (Z-phase), Mg24Y5, MgZn and a small quantity of Al-containing phase.

Topological Diversity of Coordination Polymers Containing the Rigid Terephthalate and a Flexible N,N'-Type Ligand: Interpenetration, Polyrotaxane, and Polythreading

Reactions of zinc(II) or cadmium(II) salts with terephthalic acid (H(2)tp) and 1,3-bis(4-pyridyl) propane (bpp) have afforded four coordination polymers at room temperature, [Zn(mu-tp)(mu-bpp)](n)center dot 2nH(2)O (1), [Cd-2(mu-tp)(2)(mu-bpp)(3)](n)center dot 2nH(2)O (2), [Cd(mu-tp)(mu-bpp)(H2O)](n)center dot nH(2)O (3), and [Cd-2(mu-tp)(mu-bpp)(2)(bpp)(2)Br-2](n) (4). Single-crystal X-ray diffraction has revealed interesting topological features for these compounds.

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x=0, 1 and 2, wt%) alloys

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x = 0, 1 and 2, wt%) alloys heat-treated at 603 K for 2 It have been investigated. T-phase (an Mg-Zn-Nd ternary phase) was observed in the Nd containing alloys. The optimal mechanical properties were obtained in the Mg-4.5Zn-1Nd alloy, and the ultimate tensile strength and yield strength were 228 and 79 MPa, respectively. Through comparing with the Mg-4.5Zn alloy, the increments of ultimate tensile strength and yield strength were 51 and 17 MPa.

Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Novel acid-base polyimides synthesized from binaphthalene dianhydrie and triphenylamine-containing diamine as proton exchange membranes

The synthesis and characterization of novel acid-base polyimide membranes for the use in polymer electrolyte membrane fuel cell is presented in this paper. The sulfonated polyimides (SPIs) bearing basic triphenylamine groups were easily synthesized using 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), sulfonated diamine of 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamines of 4,4'-diaminotriphenylamine (DATPA). The effects of the structure of the dianhydride and diamines on the properties of SPI membranes were evaluated through the study of membrane parameters including water sorption, proton conductivity, water stability, dimensional changes, and methanol permeability.

Pyrazine-containing Acene-Type Molecular Ribbons with up to 16 Rectilinearly Arranged Fused Aromatic Rings

A series of acene-type conjugated molecules(1-5) containing 2-6 pyrazine units and up to 16 rectilinearly arranged fused aromatic rings were synthesized by condensation coupling of 1,2-diamines and 1,2-diketones. The energy gap of the molecules estimated from absorption edge decreases with an increase in molecular length, indicating the well-delocalized nature of the molecules. The cyclic voltarnmetry measurements suggest that the n-type properties of these ribbonlike pyrazine derivatives are dependent on the molecular length and the number of the pyrazine units.

Synthesis, characterization, and electroluminescence of PPV copolymers containing electron and hole-transporting units

Three series of poly(phenylene vinylene) (PPV) derivatives containing hole-transporting triphenylamine derivatives [N-(4-octoxylphenyl)diphenylamine, N,N'-di(4-octyloxylphenyl)-N,N'-diphenyl-1,4-phenylenediamine, and N,N'-di(4-octoxylphenyl)-N,N'-diphenylbenzidine] (donor) and electron-transporting oxadiazole unit (2,5-diphenyl-1,3,4-oxadiazole) (acceptor) in the main chain were synthesized by improved Wittig copolymerization. The resulting donor-acceptor (D-A) polymers are readily soluble in common organic solvents, such as chloroform, dichloroethane, THF, and toluene.

Enolic Schiff base aluminum complexes and their catalytic stereoselective polymerization of racemic lactide

A series of enolic Schiff base aluminum(III) complexes LAIR (where L = NNOO-tetradentate enolic Schiff base ligand) containing ligands that differ in their steric and electronic properties were synthesized. Their single crystals showed that these complexes are five -coordinated around the aluminum center. Their coordination geometries are between square pyramidal and trigonal bipyramidal. Their catalytic properties in the solution polymerization of racemic lactide (rac-LA) were examined. The modifications in the auxiliary ligand exhibited a dramatic influence on the catalytic performance.