CARBONACEOUS PRODUCTS OF POLYMER-PALLADIUM COMPLEXES AS CATALYSTS FOR THE HYDROGENATION OF METHYL ACRYLATE

Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.

1, 1'—BIS (BENZYLSELENO) FERROCENE PLATINUM COMPLEX AS HYDROSlLYLATION CATALYST FOR OLEFINS

1, 1'--Bis(benzylseleno)ferrocene and its platinum complex were synthesized. It was found that the platinum complex was efficient catalyst for the hydrosilylation of olefins with triethoxysilane.

Friedel-Crafts Acylation Reactions Using Catalytic SbCl_5-TEBA Complex as an Efficient Catalyst

SbCl_5-TEBA (PhCH_2NEt_3Cl) complex catalyzes the Friedel-Crafts acylation reactionsefficiently.

CATALYTIC BEHAVIOR OF SILICA-SUPPORTED POLY-γ- AMINOPROPYL- SILOXANE-Co-Ru BIMETALLIC COMPLEX FOR THE HYDROFORMYLATION OF CYCLOHEXENE

The cobalt and ruthenium bimetallic complex of poly-γ-amino-propylsiloxane( abbr. as Si-CH_2-Co-Ru) was prepared, and it was found that it can catalyze the hydroformylation of cyclobexene effectively with the conversion amounting to over 90%. Cyclohexanecarboxaldehyde was first formed in the hydroformylation, and then further hydrogenated to form cylcohexanemethanol. The coversion was affected obviously by the Co/Ru ratio.When Co/Ru molar ratio was 100-150, i.e. in the very low content of noble metal Ru, the catalytic activity of Si-NH_2 -Co-Ru was also very high. The product composition was affected by CO/H_2 ratio in the reaction gas. Aldehyde can be got high selectively by controlling CO/H_2 ratio. Compared with other catalyst system, the Si-NH_2-Co-Ru catalyst has higher catalytic activity and efficiency with very low Ru/Co ratio. The total turnover number was more than 28,800 (based on the amount of ruthenium used).

Synthesis, Structure and Catalytic Activity of a Palladium(Ⅱ) Complex Based on 4-Chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol Ligand

The title complex bis{4-chloro-2-[（6-methyl-pyridin-2-ylimino）-methyl]-phenol}-palladium（Ⅱ）（C_（26）H_（20）Cl_2N_4O_2Pd） has been synthesized by the reaction of 4-chloro-2-[（6-methylpyridin- 2-ylimino）-methyl]-phenol with Pd（CH_3COO）_2, and characterized by IR spectrum and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures. The crystal belongs to the monoclinic system, space group P2_1/c with a = 4.1324（2）, b = 23.5432（16）, c = 11.8943（8） A, β = 91.238（5）o, V = 1156.93（12） ？~3, C_（26）H_（20）Cl_2N_4O_2Pd, M_r = 597.76, Z = 2, D_c = 1.716 g/cm^3, μ = 1.067 mm^（-1）, F（000） = 600, the final R = 0.0247 and w R = 0.0677（I 〉 2σ（I））. In the presence of methylaluminoxane（MAO）, the complex exhibits excellent catalytic activities（1.737×10~7 g of PNB（mol of Pd）^（-1）·h^（-1）） in the vinyl polymerization of norbornene.

Synthesis, Structure and Norbornene Polymerization Catalyzed by Nickel(Ⅱ) Complex Bearing N,O-bis(1-(6-ethylpyridin-2-ylimino)-methylenyl)naphthalen-2-ol Ligand

The title complex bis{1-{[（6-ethyl-2-pyridinyl）imino]methylenyl}-2-naphthale- nolato-N,O}-nickel（lI） （C36H32NnO2Ni） has been synthesized by the reaction of l-{[（6-ethyl-2- pyridinyl）imino]methylenyl}-2-naphthalenol with Ni（CH3COO）2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.410（4）, b = 14.382（4）, c = 18.121（6） ,A, β = 97.147（6）% V= 2950.5（16）A3, C36H32N4O2Ni, Mr = 611.37, Z = 4, Dc = 1.376 g/cm3, μ = 0.698 mm-1 F（000） = 1280, the final R = 0.0519 and wR = 0.1493 （1 〉2σ（I））. This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98 × 107 g ofPNB （mol of Ni）-1 h-1 with high monomer conversion.

A Novel Phenoxyimine-based Schiff Base Ligand and Its Mononuclear Nickel(Ⅱ) Complex：Synthesis,Crystal Structure,Norbornene Polymerization and Catalytic Activity

A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C（58）H（52）N2NiO2]（L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde） has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ^1H NMR and ^（13）C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 14.510（6）, b = 18.573（7）, c = 20.961（6） A, β = 123.453（19）°, V = 4713（3）A^3, Mr = 867.73, Z = 4, Dc = 1.223 g/cm^3, μ = 0.456 mm^-1, F（000） = 1832, the final R = 0.0685 and wR = 0.1758（I 〉 2σ（I））. The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10^7 g of PNB（mol of Ni）^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.

OXIDATIVE ETHOXYCARBONYLATION OF ANILINE TO ETHYL PHENYLCARBAMATE CATALYZED BY SILICA- SUPPORTED POLY-γ-AMINOPROPYLSILOXANEMETAL COMPLEXES

Several silica-supported poly-γ-aminopropylsiloxane-monometal and bimetal complexes (Si-NH_2-M,M = Cu or Co ; Si-NH_2-Cu-M', M' =Co, Sn, Mn, Ni or Fe) have been prepared. Their catalytic properties for oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate have been investigated.The catalytic reaction was carried out under relatively mild conditions. The catalyst Si-NH_2-Cu-CO had high activity and selectivity, and the turn-over number (molar of aniline converted/molar of metal in Si-NH_2-Cu-CO added) could amount to 450 under the conditions: 150℃ , 4 MPa (CO/O_2 =3) and 40 hours.The results of XPS and IR indicated that the coordination bonds were formed between nitrogen and metals in Si-NH2-Cu, Si-NH_2-Co and Si-NH_2-Cu-Co, and the coordination pattern was not single. In the oxidative ethoxycarbonylation of aniline to ethyl phenylcarbamate, the catalytic property of Si-NH_2-Cu-CO bimetallic complex was better than Si-NH_2-Cu or Si-NH_2-Co monometatlic complex. This indicated that there as synergistic action between different metals in the bimetallic complex.

Synthesis, Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,OBis{1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} Ligand

The title complex bis{1-[[（3-methyl-pyridin-2-yl） amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium（C_（42）H_（56）O_2N_4Pd） has been synthesized by the reaction of 1-[[（3-methyl-pyridin-2-yl）amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd（OAc）_2, and was characterized by IR and elemental analyses（C, H, N）. Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P1 with a = 12.3870（13）, b = 12.9673（12）, c = 14.3998（4） ？, α = 67.53（2）, β = 75.34（2）, γ = 86.89（3）°, V = 2065.5（3） A3, M_r = 773.32, Z = 2, D_c = 1.243 g/cm^3, μ = 0.489 mm^（-1）, F（000） = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene（NB） vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 10~7 g of PNB（mol of Pd）^（-1） h^（-1） with high monomer conversion using methylaluminoxane（MAO） as the cocatalyst.

COMPLEX REACTIONS OF ETHYL-GLUCOSIDES SYNTHESIS OVER ION EXCHANGE RESIN

The glycosidation reactions of D-glucose with ethanol have been carried out over a reusable and separable heterogeneous catalyst, namely, ion exchange resin. Detailed kinetic data for these reactions are reported. A complex reaction model has been developed for interpreting the data. The reactions were found to be global second-order reactions and first -order with respect to each component. Meanwhile, a new regression method is applied to determine the rate constant from time-dependent profiles.

Selective Oxidation of Isobutylene over Cs-promoted Mo-Bi-Co-Fe-Ce-O Catalyst

Cs-promoted Mo-Bi-Co-Fe-Ce-O catalyst for the selective oxidation of isobutylene to methacrolein had been studied in a fixed bed micro-reactor. The selectivity to methacrolein was significantly improved by the addition of Cs, which could probably enhance the dehydrogenation ability and weaken the oxygenation ability of the catalyst based on temperature programmed reduction （TPR） analysis investigation. The kinetic studies indicated that the oxidation of isobutylene to methacrolein followed the first-order kinetic behavior.

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce com-plex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80°C)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,COD_(Cr),and TOC removal efficiencies in the solution exceed 98.5%using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

A silica gel supported cobalt(Ⅱ) Schiff base complex as efficient and recyclable heterogeneous catalyst for the selective aerobic oxidation of alkyl aromatics

A silica gel supported cobalt（lI） Schiff base complex was synthesized and used for the oxidation of alkyl aromatics using molecular oxygen as an oxidant under atmosphere pressure. The catalyst shows a high conversion of alkyl aromatics and selectivity to benzylic ketones, and could be reused at least 5 times without significant loss of catalytic activity.

Zinc bis-Schiff base complexes： Synthesis, structure, and application in ring-opening polymerization of rac-lactide

A series of bis-ligated zinc complexes supported by Schitt base ligands were successfully synthesized and characterized by 1 H, 13C NMR, elemental analysis, and X-ray crystallography. These zinc complexes can be used as catalysts for the polymerization of rac-lactide in solution as well as in molten lactide. The results show that all catalysts exhibited high catalytic activity and obtained moderate heterotactic PLAs with the expected molecular weight. Complex 1 can catalyze the polymerization of rac-lactide under controllable conditions with living and immortal character in toluene solution. In addition, the steric hindrance and electronic effects has a great influence on the catalytic activity and selectivity of catalysts.