The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylatio...The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The influences of temperature, amount of platinum complexes used and the nature of olefins used on the catalytic activity of the complexes are also investigated in this paper.展开更多
The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with differen...The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.展开更多
A new stable salen Schiff base cobalt and crown ether sodium complex （SalCo-NaB18C6） was prepared through copolymerization. This copolymer complex was applied to catalytic oxidation of hydrocarbon compound with mole...A new stable salen Schiff base cobalt and crown ether sodium complex （SalCo-NaB18C6） was prepared through copolymerization. This copolymer complex was applied to catalytic oxidation of hydrocarbon compound with molecular oxygen without reductant, which was shown the higher activity and selectivity for ketone, and reused effectively.展开更多
The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurement...The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.展开更多
Introduction The study of metal complexes with the crown ether is a quite interesting research field, but the research has mainly focused on the metal complexes with some crown ethers with a relatively small cavity su...Introduction The study of metal complexes with the crown ether is a quite interesting research field, but the research has mainly focused on the metal complexes with some crown ethers with a relatively small cavity such as 12-crown-4, 15-crown-5 and 18- crown-6 as well as their derivatives. Crown ethers with a larger cavity contain more oxygen atoms, so they have the ability to form the complexes of a higher co-展开更多
Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownethe...Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.展开更多
ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder s...ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.展开更多
Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxy...Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.展开更多
A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemic...A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.展开更多
The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, bu...The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinatewith platinum compound, and the platinum complex is a new kind of catalyst for thehydrosilylation of olefins with triethoxysilane.展开更多
Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6...Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.展开更多
Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,B...Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.展开更多
Novel Co（Ⅱ） complexes with dihydroxamic acids functionalized N-pivot lariat ether CoL^1-CoL^4 were synthesized and characterized.Their oxygenation constants（ln K_（O2）） and thermodynamic parameters（△H°,△...Novel Co（Ⅱ） complexes with dihydroxamic acids functionalized N-pivot lariat ether CoL^1-CoL^4 were synthesized and characterized.Their oxygenation constants（ln K_（O2）） and thermodynamic parameters（△H°,△S°） were measured.And their catalytic performance in oxidation of p-xylene to p-toluic acid（PTA） was investigated.The enhancement of O_2-binding and catalytic oxidation activity by the oxa aza crown ether ring of the cobalt complexes were discussed.展开更多
A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP ...A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.展开更多
Under given conditions, two complexes of [Ni（H20）2BEDA]·2H2O 1 and [Ni（Py）2- BEDA]·6H2O 2 （BEDA = bis（3-methoxy-2-pyridyl）ether-6,6′-dicarboxylic acid） have been synthesized and characterized by ele...Under given conditions, two complexes of [Ni（H20）2BEDA]·2H2O 1 and [Ni（Py）2- BEDA]·6H2O 2 （BEDA = bis（3-methoxy-2-pyridyl）ether-6,6′-dicarboxylic acid） have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Crystal data for 1： C14H18NiN2O11, monoelinic C2/c, a = 14.3844（17）, b = 12.9900（15）, c = 9.6309（11） A, β = 104.3350（10）°, V= 1743.5（4） A3, Z = 4, Dc= 1.711 g/cm^3, F（000） = 928, μ = 1.179 mm^-1, Mr= 449.01, the final R = 0.0228 and wR = 0.0625. Crystal data for 2： C24H32NiN4O13, triclinic P1, a = 9.423（2）, b = 11.863（3）, c = 13.089（3） A, α = 91.511（3）, β = 92.465（3）, γ = 100.696（2）°, V = 1435.6（6） A^3, Z = 2, Dc= 1.488 g/cm^3, F（000） = 672, μ = 0.748 mm^-1, Mr= 643.25, the final R = 0.0400 and wR = 0.0975. Interestingly, in the two complexes, lattice water molecules dominate its crystal structures. Therefore, extensive intermolecular hydrogen bonds assemble 1 and 2 into 2D extended sheets and a 3D open framework, respectively. Furthermore, water molecules present in 2 are associated to form water clusters.展开更多
The formation of charge transfer complex between iodine with 4＇-nitrobenzo-15-crown-5（NB15C5） and benzo-15-crown-5 （B15C5） is investigated spectrophotometrically in chloroform and dichloromethane（DCM） solutions...The formation of charge transfer complex between iodine with 4＇-nitrobenzo-15-crown-5（NB15C5） and benzo-15-crown-5 （B15C5） is investigated spectrophotometrically in chloroform and dichloromethane（DCM） solutions at 25℃.The pseudo-first-order rate constants for the transformation process were evaluated from the absorbance-time data and found to vary in the order of DCM CHCl_3.The values of the formation constant,K_f,for each complex are evaluated from Benesi-Hilebrand equation. Stability of the resulting complex in two solvents was also found to vary in the order of DCM CHCl_3.展开更多
Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the dope...Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.展开更多
基金Supported by the Fund for Ph.D. programme from State Education Commission
文摘The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The influences of temperature, amount of platinum complexes used and the nature of olefins used on the catalytic activity of the complexes are also investigated in this paper.
基金the National Natural Science Foundation of China (29872034) and the Natural Science Foundation of Henan Province for the financi
文摘The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.
基金the National Natural Science Foundation of China （No.20274034）.
文摘A new stable salen Schiff base cobalt and crown ether sodium complex （SalCo-NaB18C6） was prepared through copolymerization. This copolymer complex was applied to catalytic oxidation of hydrocarbon compound with molecular oxygen without reductant, which was shown the higher activity and selectivity for ketone, and reused effectively.
文摘The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.
文摘Introduction The study of metal complexes with the crown ether is a quite interesting research field, but the research has mainly focused on the metal complexes with some crown ethers with a relatively small cavity such as 12-crown-4, 15-crown-5 and 18- crown-6 as well as their derivatives. Crown ethers with a larger cavity contain more oxygen atoms, so they have the ability to form the complexes of a higher co-
文摘Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.
文摘ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.
文摘Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.
文摘A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.
基金This work was supported by the National Natural Science Foundation of China
文摘The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinatewith platinum compound, and the platinum complex is a new kind of catalyst for thehydrosilylation of olefins with triethoxysilane.
文摘Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.
文摘Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.
基金supported by Chongqing Education Commission(No.KJ1400632)
文摘Novel Co（Ⅱ） complexes with dihydroxamic acids functionalized N-pivot lariat ether CoL^1-CoL^4 were synthesized and characterized.Their oxygenation constants（ln K_（O2）） and thermodynamic parameters（△H°,△S°） were measured.And their catalytic performance in oxidation of p-xylene to p-toluic acid（PTA） was investigated.The enhancement of O_2-binding and catalytic oxidation activity by the oxa aza crown ether ring of the cobalt complexes were discussed.
文摘A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.
基金supported by the Henan Innovation Project for University Prominent Research Talents (No. 2005KYCX021)Natural Science Foundation of Henan Province (No. 082300420040)
文摘Under given conditions, two complexes of [Ni（H20）2BEDA]·2H2O 1 and [Ni（Py）2- BEDA]·6H2O 2 （BEDA = bis（3-methoxy-2-pyridyl）ether-6,6′-dicarboxylic acid） have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Crystal data for 1： C14H18NiN2O11, monoelinic C2/c, a = 14.3844（17）, b = 12.9900（15）, c = 9.6309（11） A, β = 104.3350（10）°, V= 1743.5（4） A3, Z = 4, Dc= 1.711 g/cm^3, F（000） = 928, μ = 1.179 mm^-1, Mr= 449.01, the final R = 0.0228 and wR = 0.0625. Crystal data for 2： C24H32NiN4O13, triclinic P1, a = 9.423（2）, b = 11.863（3）, c = 13.089（3） A, α = 91.511（3）, β = 92.465（3）, γ = 100.696（2）°, V = 1435.6（6） A^3, Z = 2, Dc= 1.488 g/cm^3, F（000） = 672, μ = 0.748 mm^-1, Mr= 643.25, the final R = 0.0400 and wR = 0.0975. Interestingly, in the two complexes, lattice water molecules dominate its crystal structures. Therefore, extensive intermolecular hydrogen bonds assemble 1 and 2 into 2D extended sheets and a 3D open framework, respectively. Furthermore, water molecules present in 2 are associated to form water clusters.
文摘The formation of charge transfer complex between iodine with 4＇-nitrobenzo-15-crown-5（NB15C5） and benzo-15-crown-5 （B15C5） is investigated spectrophotometrically in chloroform and dichloromethane（DCM） solutions at 25℃.The pseudo-first-order rate constants for the transformation process were evaluated from the absorbance-time data and found to vary in the order of DCM CHCl_3.The values of the formation constant,K_f,for each complex are evaluated from Benesi-Hilebrand equation. Stability of the resulting complex in two solvents was also found to vary in the order of DCM CHCl_3.
基金Project supported by the National Natural Science Foundation of China (20461002) Chun Hui Plan Foundation of MOE(Z2004-2-15029)
文摘Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.
