A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes...A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ(MoKα) = 1.422 mm-1, F(000) = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper(H) centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper(Ⅱ) ion and shares the other phenolate group between the two copper(H) ions, affording a Cu2O2 plane. Each copper(Ⅱ) center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data (2-300 K) of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑(Xobsd -Xcalcd)2/∑Xobsd2= 2.76 × 10^-3.展开更多
Polyolefins,as one of the most productive synthetic polymer materials,have been widely used in industry and daily life[1-2].However,due to their"non-polar"nature,polyolefins have poor compatibility and adhes...Polyolefins,as one of the most productive synthetic polymer materials,have been widely used in industry and daily life[1-2].However,due to their"non-polar"nature,polyolefins have poor compatibility and adhesion to polar materials,limiting their application in many fields[3-5].展开更多
The self-assembled formation of a one-dimensional lanthanum salicylald imine coordination polymer was proved by the X-ray diffraction analysis of new l anthanum(Ⅲ) nitrate complex containing N,N’-bis(salicylidene)-1...The self-assembled formation of a one-dimensional lanthanum salicylald imine coordination polymer was proved by the X-ray diffraction analysis of new l anthanum(Ⅲ) nitrate complex containing N,N’-bis(salicylidene)-1,5-pentanediami ne ligand(H2L) . It was obtained in situ in a one-step,metal-templated condensa tion of salicylaldehyde with 1,5-pentanediamine(cadaverine,biogenic polyamine) and characterized by microanalysis and spectroscopic(IR,ESI-MS,UV-Vis,and 1 H NMR) data. The [La(NO3) 3(μ-H2L) 2]∞ complex displayed 10-coordinate distorted bicapped dodecahedron geometry with unusual coordination pattern of undeprotonat ed salicylaldimines which acted as μ-bridging ditopic ligands using exclusivel y the oxygens as donor atoms with the nitrogen atoms not being involved in the c oordination environment.展开更多
A series of salicylaldimine ligands were designed to promote the copper-catalyzed Ullmann cross- coupling reaction. After a screening process, 2-((2-isopropylphenylimino)methyl)phenol was found to serve as a good ...A series of salicylaldimine ligands were designed to promote the copper-catalyzed Ullmann cross- coupling reaction. After a screening process, 2-((2-isopropylphenylimino)methyl)phenol was found to serve as a good supporting ligand for this reaction. Employing this Schiff-base ligand as a new supporting ligand, the copper-catalyzed coupling reactions of aryl bromides and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. Various diaryl ethers were obtained with excellent yields in dioxane in the presence of K3P04 and a catalytic amount of copper(I) salt.展开更多
The title nickel complex (C34H3oCl2N2NiO4, Mr = 660.21) has been synthesized and its crystal structure was determined by single-crystal X-ray structure analysis. It crystallizes in the monoclinic system, space group...The title nickel complex (C34H3oCl2N2NiO4, Mr = 660.21) has been synthesized and its crystal structure was determined by single-crystal X-ray structure analysis. It crystallizes in the monoclinic system, space group P21/n with a = 11.026(8), b = 11.491(8), c = 12.119(9) A°, β=91.328(13)°, Z= 2, V= 1535.0(19) ,A°^3, Dc = 1.428 g/cm^3, F(000) = 684 andμ(MoKa) = 0.848 mm^-1 The structure was refined to R = 0.0544 for 1813 observed reflections with I 〉 2σ(I) and wR =0.0867 for 3132 unique reflections. The molecule of the complex is high symmetrical. Ni(Ⅱ) atom is located in the symmetric center and coordinated to two phenolic oxygen and two imino nitrogen atoms, forming two six-membered rings. Upon activation with methylaluminoxane (MAO), it is active for ethylene oligomerization.展开更多
Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives.Nevertheless,for such catalytic systems,insoluble polynorbornene(PNB)products are often produced which hampers t...Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives.Nevertheless,for such catalytic systems,insoluble polynorbornene(PNB)products are often produced which hampers their further detailed characterizations,such as molecular weights,polydispersities,stereoregularities,etc.In this work,we surprisingly found that for a traditional Ni(acac)_(2)/MAO system that was previously reported to give insoluble PNBs,incorporation of highly bulk salicylaldiminate ligands could significantly improve the solubility of the PNBs in common organic solvents,which allowed for subsequent thorough detailed analysis of the polymer products.Moreover,it was also observed that high-temperature polymerization was beneficial for further improving the PNB’s solubilities due to the decreased molecular weights and stereoregularities.Different ligand skeletons and ligand equivalents were also investigated to give a comprehensive view of their influences on the polymers’solubilities,and based on these results,a plausible mechanism that caused such a big difference was tentatively proposed.展开更多
A series of N-(5-chloro-2-hydroxyphenyl)-(3/4/5-substituted)-salicylaldimines (I--XI) were synthesized using appropriate synthetic route. Their structures were characterized by FT-IR, UV-Visible, ESI-MS, 1H and ...A series of N-(5-chloro-2-hydroxyphenyl)-(3/4/5-substituted)-salicylaldimines (I--XI) were synthesized using appropriate synthetic route. Their structures were characterized by FT-IR, UV-Visible, ESI-MS, 1H and 13C NMR spectroscopic techniques and analytical methods. The crystal structure of N-(5-chloro-2-hydroxyphenyl)-5-bromo- salicylaldimine (V) was determined by X-ray diffraction at room temperature. Relationship between the melting points and the structures of the compounds was examined. Antimicrobial activity of the compounds was evaluated against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Proteus mirabilis. Antifungal activities were reported for Candida albicans. Schiff bases showed considerable antimicrobial activity against S. aureus, S, epidermidis and C. albicans. N-(5-Chloro-2-hydroxyphenyl)-3-hydroxy-salieylaldimine (II) has the broadest and highest antimicrobial activity according to the others.展开更多
A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling mode...A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.展开更多
基金supported by the Natural Science Research Program of the Education Department of Hebei Province (No. Z2008107)the National Natural Science Foundation of China (No. 20601014)the National Basic Research Program of China (973 Program, 2007CB815305)
文摘A new dinuclear copper(Ⅱ) complex, [Cu(L)(py)]2 1 (H2L = N-(2-hydroxybenzyl)- salicylaldimine, py = pyridine), has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ(MoKα) = 1.422 mm-1, F(000) = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper(H) centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper(Ⅱ) ion and shares the other phenolate group between the two copper(H) ions, affording a Cu2O2 plane. Each copper(Ⅱ) center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data (2-300 K) of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑(Xobsd -Xcalcd)2/∑Xobsd2= 2.76 × 10^-3.
基金This work was supported by the National Natural Science Foundation of China(No.22001004)。
文摘Polyolefins,as one of the most productive synthetic polymer materials,have been widely used in industry and daily life[1-2].However,due to their"non-polar"nature,polyolefins have poor compatibility and adhesion to polar materials,limiting their application in many fields[3-5].
基金Project supported by the Polish Ministry of Science and Higher Education (NN204 0317 33)
文摘The self-assembled formation of a one-dimensional lanthanum salicylald imine coordination polymer was proved by the X-ray diffraction analysis of new l anthanum(Ⅲ) nitrate complex containing N,N’-bis(salicylidene)-1,5-pentanediami ne ligand(H2L) . It was obtained in situ in a one-step,metal-templated condensa tion of salicylaldehyde with 1,5-pentanediamine(cadaverine,biogenic polyamine) and characterized by microanalysis and spectroscopic(IR,ESI-MS,UV-Vis,and 1 H NMR) data. The [La(NO3) 3(μ-H2L) 2]∞ complex displayed 10-coordinate distorted bicapped dodecahedron geometry with unusual coordination pattern of undeprotonat ed salicylaldimines which acted as μ-bridging ditopic ligands using exclusivel y the oxygens as donor atoms with the nitrogen atoms not being involved in the c oordination environment.
基金the National Natural Science Foundation of ChinaKey Laboratory of Organic Synthesis of Jiangsu Province for the financial support(Nos.21201147,21302063,KJS1112)
文摘A series of salicylaldimine ligands were designed to promote the copper-catalyzed Ullmann cross- coupling reaction. After a screening process, 2-((2-isopropylphenylimino)methyl)phenol was found to serve as a good supporting ligand for this reaction. Employing this Schiff-base ligand as a new supporting ligand, the copper-catalyzed coupling reactions of aryl bromides and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. Various diaryl ethers were obtained with excellent yields in dioxane in the presence of K3P04 and a catalytic amount of copper(I) salt.
基金This work was supported by the National Natural Science Foundation of China (No. 20272062 and 20473099) and National 863 Project (2002AA333060)
文摘The title nickel complex (C34H3oCl2N2NiO4, Mr = 660.21) has been synthesized and its crystal structure was determined by single-crystal X-ray structure analysis. It crystallizes in the monoclinic system, space group P21/n with a = 11.026(8), b = 11.491(8), c = 12.119(9) A°, β=91.328(13)°, Z= 2, V= 1535.0(19) ,A°^3, Dc = 1.428 g/cm^3, F(000) = 684 andμ(MoKa) = 0.848 mm^-1 The structure was refined to R = 0.0544 for 1813 observed reflections with I 〉 2σ(I) and wR =0.0867 for 3132 unique reflections. The molecule of the complex is high symmetrical. Ni(Ⅱ) atom is located in the symmetric center and coordinated to two phenolic oxygen and two imino nitrogen atoms, forming two six-membered rings. Upon activation with methylaluminoxane (MAO), it is active for ethylene oligomerization.
基金financially supported by the National Natural Science Foundation of China(Nos.21801236 and U1862206)。
文摘Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives.Nevertheless,for such catalytic systems,insoluble polynorbornene(PNB)products are often produced which hampers their further detailed characterizations,such as molecular weights,polydispersities,stereoregularities,etc.In this work,we surprisingly found that for a traditional Ni(acac)_(2)/MAO system that was previously reported to give insoluble PNBs,incorporation of highly bulk salicylaldiminate ligands could significantly improve the solubility of the PNBs in common organic solvents,which allowed for subsequent thorough detailed analysis of the polymer products.Moreover,it was also observed that high-temperature polymerization was beneficial for further improving the PNB’s solubilities due to the decreased molecular weights and stereoregularities.Different ligand skeletons and ligand equivalents were also investigated to give a comprehensive view of their influences on the polymers’solubilities,and based on these results,a plausible mechanism that caused such a big difference was tentatively proposed.
文摘A series of N-(5-chloro-2-hydroxyphenyl)-(3/4/5-substituted)-salicylaldimines (I--XI) were synthesized using appropriate synthetic route. Their structures were characterized by FT-IR, UV-Visible, ESI-MS, 1H and 13C NMR spectroscopic techniques and analytical methods. The crystal structure of N-(5-chloro-2-hydroxyphenyl)-5-bromo- salicylaldimine (V) was determined by X-ray diffraction at room temperature. Relationship between the melting points and the structures of the compounds was examined. Antimicrobial activity of the compounds was evaluated against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Proteus mirabilis. Antifungal activities were reported for Candida albicans. Schiff bases showed considerable antimicrobial activity against S. aureus, S, epidermidis and C. albicans. N-(5-Chloro-2-hydroxyphenyl)-3-hydroxy-salieylaldimine (II) has the broadest and highest antimicrobial activity according to the others.
基金financially supported by the National Natural Science Foundation of China(Nos.U1862206 and 21801236)。
文摘A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.