Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liq...Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liquids 1-methyl-3-（4-sulfonic acid）butylimidazolium hydrosulfate [MIm（CH2）4803H][HSO4] and 1-methyl-3-（4-sulfonic acid）butylimidazolium triflate [MIm（CH2）4SO3H][OTf] were firstly employed as cocatalysts instead of these Lewis acid and Brφnsted acids. By using a ligand-free and weak corrosive catalyst in situ prepared form PdBr2, LiBr.H2O, and [MIm（CH2）4SO3H][OTf], the arnidocarbo- nylation of benzaldehyde, acetamide, and CO could proceed smoothly and afford N-acetyl-α-phenylglycine with yield of 58% in [C6mim]PF6 medium.展开更多
Highly dispersed palladium nanoparticles were synthesized in the presence of immobilized ionic liquid on mesoporous silica SBA-15.PdNPs(2.4 nm)_me-Im@SBA-15 catalyst was prepared by the reduction using NaBH_4 as the r...Highly dispersed palladium nanoparticles were synthesized in the presence of immobilized ionic liquid on mesoporous silica SBA-15.PdNPs(2.4 nm)_me-Im@SBA-15 catalyst was prepared by the reduction using NaBH_4 as the reducing agent with controlled feed rate and has been investigated as ligand-free catalyst for Suzuki–Miyaura cross-coupling reaction at room temperature in aqueous solution under air.PdNPs catalyst was also prepared in situ from PdCl4_me-Im@SBA-15 during the reaction and demonstrated high activity and stability towards nitrobenzene hydrogenation at high temperature. Both catalysts were reusable at least for four recycle processes without significant loss in activity with simple procedure. The catalysts were characterized by TEM, EXAFS, FTIR and XPS.展开更多
Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex （promoted by ultrasonic and microwave in ionic liquid of ...Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex （promoted by ultrasonic and microwave in ionic liquid of [bmim][BF4I） were performed with high yield and good regioselectivity. This method has advantages of environmentally benign, generality, simplicity and potential for recycling of ionic liquid and catalyat.展开更多
The electrochemical behavior of Pd(Ⅱ) and Rh(Ⅲ) in [EMIm]NTf2ionic liquid has been studied on Pt working electrodes at 298 K by cyclic voltammetry(CV), polarization curve and galvanostatic transient techniques.Cycli...The electrochemical behavior of Pd(Ⅱ) and Rh(Ⅲ) in [EMIm]NTf2ionic liquid has been studied on Pt working electrodes at 298 K by cyclic voltammetry(CV), polarization curve and galvanostatic transient techniques.Cyclic voltammogram of Pd(II) in [EMIm]NTf2consists of two cathodic current peaks located at 1.37 V(E pc2),corresponding to Pd2+/Pd+, and at 0.69 V(E pc1) corresponding to Pd+/Pd. The transfer coefficient α was calculated by the Tafel extrapolation from the polarization curves to be 0.306, which is in agreement with the value reported in an aqueous solution system. For Rh(Ⅲ) in [EMIm]NTf2, a cathodic current peak(E pc) was observed at-0.39 V, corresponding to Rh3+/Rh, and two oxidation peaks were observed at-0.13 V(E pa1) and0.37 V(E pa2) during the reverse scan. A significantly negative shift in the cathodic peak potential was observed with the increase of the scan rate, indicating that the reduction of Pd(II) and Rh(Ⅲ) on the Pt electrode involves kinetic complications. By using the galvanostatic transient technique, the diffusion coefficients of Pd(II) and Rh(Ⅲ) in [EMIm]NTf2ionic liquid solution were found to be ～ 10-7cm2/s. The potential difference between the reduction of Pd(II) to Pd and the reduction of Rh(Ⅲ) to Rh obtained from the CV curves of the Pd(II) and Rh(Ⅲ) co-existing [EMIm]NTf2solution is found to be about 0.74 V, which makes it possible to electrodeposit Pd(II) and Rh(Ⅲ) separately.展开更多
基金the National Natural Science Foundation of China(No.20343005,20473107,20673130,and 20773147).
文摘Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liquids 1-methyl-3-（4-sulfonic acid）butylimidazolium hydrosulfate [MIm（CH2）4803H][HSO4] and 1-methyl-3-（4-sulfonic acid）butylimidazolium triflate [MIm（CH2）4SO3H][OTf] were firstly employed as cocatalysts instead of these Lewis acid and Brφnsted acids. By using a ligand-free and weak corrosive catalyst in situ prepared form PdBr2, LiBr.H2O, and [MIm（CH2）4SO3H][OTf], the arnidocarbo- nylation of benzaldehyde, acetamide, and CO could proceed smoothly and afford N-acetyl-α-phenylglycine with yield of 58% in [C6mim]PF6 medium.
基金the financial support from the Institute for Quantum Chemical Exploration(IQCE)
文摘Highly dispersed palladium nanoparticles were synthesized in the presence of immobilized ionic liquid on mesoporous silica SBA-15.PdNPs(2.4 nm)_me-Im@SBA-15 catalyst was prepared by the reduction using NaBH_4 as the reducing agent with controlled feed rate and has been investigated as ligand-free catalyst for Suzuki–Miyaura cross-coupling reaction at room temperature in aqueous solution under air.PdNPs catalyst was also prepared in situ from PdCl4_me-Im@SBA-15 during the reaction and demonstrated high activity and stability towards nitrobenzene hydrogenation at high temperature. Both catalysts were reusable at least for four recycle processes without significant loss in activity with simple procedure. The catalysts were characterized by TEM, EXAFS, FTIR and XPS.
文摘Synthesis of 3-naphthylcyclohexene by the Heck reactions of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladiun and nickel complex （promoted by ultrasonic and microwave in ionic liquid of [bmim][BF4I） were performed with high yield and good regioselectivity. This method has advantages of environmentally benign, generality, simplicity and potential for recycling of ionic liquid and catalyat.
基金Supported by the National Natural Science Foundation of China(Nos.91026019 and 91126006)
文摘The electrochemical behavior of Pd(Ⅱ) and Rh(Ⅲ) in [EMIm]NTf2ionic liquid has been studied on Pt working electrodes at 298 K by cyclic voltammetry(CV), polarization curve and galvanostatic transient techniques.Cyclic voltammogram of Pd(II) in [EMIm]NTf2consists of two cathodic current peaks located at 1.37 V(E pc2),corresponding to Pd2+/Pd+, and at 0.69 V(E pc1) corresponding to Pd+/Pd. The transfer coefficient α was calculated by the Tafel extrapolation from the polarization curves to be 0.306, which is in agreement with the value reported in an aqueous solution system. For Rh(Ⅲ) in [EMIm]NTf2, a cathodic current peak(E pc) was observed at-0.39 V, corresponding to Rh3+/Rh, and two oxidation peaks were observed at-0.13 V(E pa1) and0.37 V(E pa2) during the reverse scan. A significantly negative shift in the cathodic peak potential was observed with the increase of the scan rate, indicating that the reduction of Pd(II) and Rh(Ⅲ) on the Pt electrode involves kinetic complications. By using the galvanostatic transient technique, the diffusion coefficients of Pd(II) and Rh(Ⅲ) in [EMIm]NTf2ionic liquid solution were found to be ～ 10-7cm2/s. The potential difference between the reduction of Pd(II) to Pd and the reduction of Rh(Ⅲ) to Rh obtained from the CV curves of the Pd(II) and Rh(Ⅲ) co-existing [EMIm]NTf2solution is found to be about 0.74 V, which makes it possible to electrodeposit Pd(II) and Rh(Ⅲ) separately.
