A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed t...A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed that the catalyst could catalyze the reaction in95.6% conversion with 92.8% selectivity for the normal aldehyde, methyl β-formylisobu-tyrate. Such catalyst also showed high stability during the reaction and could be used repeat-edly.展开更多
Tetranuclear Rh-Co bimetallic cluster was synthesized and characterized by IR and XPS. The properties of the anchored catalysts, its stability and the ligand effect were also studied. The experimental results show tha...Tetranuclear Rh-Co bimetallic cluster was synthesized and characterized by IR and XPS. The properties of the anchored catalysts, its stability and the ligand effect were also studied. The experimental results show that the optimal conditions for the hydroformylation of hexene-1 are as follows: the temperature is 80℃, reaction time 8 h, pressure 5. 88×105 Pa, and molar ratio of H2/CO 1. 2/1. 0. Functional groups attached to the donor atom(N) possess more or less some influence on the catalytic behavior. Compared with the homogeneous cluster, the polymer-supported bimetallic cluster is more stable. After the catalytic reaction, the structure of the anchored catalysts was not destroyed. X-ray photoelectron spectroscopy characterization indicates that there is a weak interaction between the polymer support and the active metals.展开更多
By the reactions of [Rh2Co2(CO)12] 1 with functionally substituted alkyne ligands HC≡CR 2 (R = FeCp2) and 3 (R = 2-OH-C6H4COOCH2), respectively in n-hexane at room temperature, two new cluster derivatives [Rh2Co2(CO)...By the reactions of [Rh2Co2(CO)12] 1 with functionally substituted alkyne ligands HC≡CR 2 (R = FeCp2) and 3 (R = 2-OH-C6H4COOCH2), respectively in n-hexane at room temperature, two new cluster derivatives [Rh2Co2(CO)6(-CO)4(4, 2-HC≡CR)] 4 (R = FeCp2) and 5 (R = 2-OH-C6H4COOCH2) were obtained respectively. The alkyne was inserted into the CoCo bond of cluster 1 to give two butterfly clusters. Cluster 4 has been determined by single-crystal X-ray diffraction. Crystallographic data: C22H10Co2FeO10Rh2, Mr = 813.83, orthorhombic, space group P212121, a = 11.5318(7), b = 12.6572(7), c = 17.018(1) ? V = 2483.9(3) 3, Z = 4, Dc = 2.176 g/cm3, F(000) = 1568, = 3.233 mm-1, the final R = 0.0366 and wR = 0.0899 for 5367 observed reflections with I > 2(I). The two clusters have also been characterized by elemental analysis, IR and 1H-NMR spectroscopy.展开更多
The synthesis and spectrophotometric properties of 2-(6-methyl-2-benzothiazolylazo)-5-diethylamino phenol (MBTAE), and the use of it as a precolumn derivatizing reagent to separate Co(Ⅱ), Ni(Ⅱ), Rh(Ⅲ) and Ir( Ⅳ) c...The synthesis and spectrophotometric properties of 2-(6-methyl-2-benzothiazolylazo)-5-diethylamino phenol (MBTAE), and the use of it as a precolumn derivatizing reagent to separate Co(Ⅱ), Ni(Ⅱ), Rh(Ⅲ) and Ir( Ⅳ) complexes by HPLC are discussed. When the mobile phase consists of methanol/water(90/10 Ⅴ/Ⅴ), acetate buffer with pH 4. 0 and 5×10-5 mol/L EDTA solution, the four complexes Can be separated within 9 min on ODS column. The detection limits (20 μL sample size) are 0. 059 ppb, 0. 062 ppb, 0. 053 ppb and 0. 049 ppb for Co(Ⅱ) , Rh(Ⅲ), Ni(Ⅱ) and lr(Ⅳ) respectively at a signal-to-noise ratio of 3.展开更多
The octahedral cluster complex Rh 2Co 2(CO) 10(μ 4, η2 -HC≡CFc) 1 reacts with PPh 3 to give the title cluster Rh 2Co 2(CO) 10-n(μ 4, η2-HC≡CFc)(PPh 3) n(2, n=1; 3, n=2, ). The structure of 3 has been determined ...The octahedral cluster complex Rh 2Co 2(CO) 10(μ 4, η2 -HC≡CFc) 1 reacts with PPh 3 to give the title cluster Rh 2Co 2(CO) 10-n(μ 4, η2-HC≡CFc)(PPh 3) n(2, n=1; 3, n=2, ). The structure of 3 has been determined by X-ray diffraction. At 60 ℃ and 1.8 MPa of initial total CO/H 2 (1∶1) pressure, the catalytic activity of 3 for hydroformylation of s tyrene has also been investigated. The conversion of the styrene is 98.1%, the selectivity of the aldehydes is 99%, the 3-phenylpropyl aldehyde(n)/2-phenylpropyl aldehyde( i) mole ratio of aldehyde to 1/17.4.展开更多
文摘A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed that the catalyst could catalyze the reaction in95.6% conversion with 92.8% selectivity for the normal aldehyde, methyl β-formylisobu-tyrate. Such catalyst also showed high stability during the reaction and could be used repeat-edly.
基金The project supported by National Natural Science Foundation of China
文摘Tetranuclear Rh-Co bimetallic cluster was synthesized and characterized by IR and XPS. The properties of the anchored catalysts, its stability and the ligand effect were also studied. The experimental results show that the optimal conditions for the hydroformylation of hexene-1 are as follows: the temperature is 80℃, reaction time 8 h, pressure 5. 88×105 Pa, and molar ratio of H2/CO 1. 2/1. 0. Functional groups attached to the donor atom(N) possess more or less some influence on the catalytic behavior. Compared with the homogeneous cluster, the polymer-supported bimetallic cluster is more stable. After the catalytic reaction, the structure of the anchored catalysts was not destroyed. X-ray photoelectron spectroscopy characterization indicates that there is a weak interaction between the polymer support and the active metals.
基金the National Natural Science Foundation of China (29871061)
文摘By the reactions of [Rh2Co2(CO)12] 1 with functionally substituted alkyne ligands HC≡CR 2 (R = FeCp2) and 3 (R = 2-OH-C6H4COOCH2), respectively in n-hexane at room temperature, two new cluster derivatives [Rh2Co2(CO)6(-CO)4(4, 2-HC≡CR)] 4 (R = FeCp2) and 5 (R = 2-OH-C6H4COOCH2) were obtained respectively. The alkyne was inserted into the CoCo bond of cluster 1 to give two butterfly clusters. Cluster 4 has been determined by single-crystal X-ray diffraction. Crystallographic data: C22H10Co2FeO10Rh2, Mr = 813.83, orthorhombic, space group P212121, a = 11.5318(7), b = 12.6572(7), c = 17.018(1) ? V = 2483.9(3) 3, Z = 4, Dc = 2.176 g/cm3, F(000) = 1568, = 3.233 mm-1, the final R = 0.0366 and wR = 0.0899 for 5367 observed reflections with I > 2(I). The two clusters have also been characterized by elemental analysis, IR and 1H-NMR spectroscopy.
基金Supported by the National Natural Science Foundation of China
文摘The synthesis and spectrophotometric properties of 2-(6-methyl-2-benzothiazolylazo)-5-diethylamino phenol (MBTAE), and the use of it as a precolumn derivatizing reagent to separate Co(Ⅱ), Ni(Ⅱ), Rh(Ⅲ) and Ir( Ⅳ) complexes by HPLC are discussed. When the mobile phase consists of methanol/water(90/10 Ⅴ/Ⅴ), acetate buffer with pH 4. 0 and 5×10-5 mol/L EDTA solution, the four complexes Can be separated within 9 min on ODS column. The detection limits (20 μL sample size) are 0. 059 ppb, 0. 062 ppb, 0. 053 ppb and 0. 049 ppb for Co(Ⅱ) , Rh(Ⅲ), Ni(Ⅱ) and lr(Ⅳ) respectively at a signal-to-noise ratio of 3.
文摘The octahedral cluster complex Rh 2Co 2(CO) 10(μ 4, η2 -HC≡CFc) 1 reacts with PPh 3 to give the title cluster Rh 2Co 2(CO) 10-n(μ 4, η2-HC≡CFc)(PPh 3) n(2, n=1; 3, n=2, ). The structure of 3 has been determined by X-ray diffraction. At 60 ℃ and 1.8 MPa of initial total CO/H 2 (1∶1) pressure, the catalytic activity of 3 for hydroformylation of s tyrene has also been investigated. The conversion of the styrene is 98.1%, the selectivity of the aldehydes is 99%, the 3-phenylpropyl aldehyde(n)/2-phenylpropyl aldehyde( i) mole ratio of aldehyde to 1/17.4.
