A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthe...A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.展开更多
A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, element...A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638（3）, b = 10.2319（3）, c = 13.2463（4） ？, α = 80.1710（10）, β = 83.671（2）, γ = 70.3790（10）o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85（6） ？3, Dc = 1.746 g/cm3, F（000） = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ（I）. In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.展开更多
A fluorescent Ni（II） complex 1, [Ni（OH-H2Bdc）（Bibimp）]n·nH2O, constructed with 5-hydroxyisophthalic acid（OH-H2Bdc） and 2,6-bis（2-benzimidazolyl）pyridine）（Bibimp） has been synthesized by hydrothermal ...A fluorescent Ni（II） complex 1, [Ni（OH-H2Bdc）（Bibimp）]n·nH2O, constructed with 5-hydroxyisophthalic acid（OH-H2Bdc） and 2,6-bis（2-benzimidazolyl）pyridine）（Bibimp） has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a = 10.187（2）, b = 10.273（2）, c = 13.401（3）A, α = 69.65（3）, β = 69.66（3）, γ = 70.61（3）°, V = 1196.8（4） A3, and Z = 2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C–H…O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.展开更多
A new α-diimine ligand 1a, bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2a, {bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene}d...A new α-diimine ligand 1a, bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2a, {bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene}dibromo- nickel were successfully synthesized, and characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscope（FTIR）, elemental analysis and X-ray photoelectron spectroscopy（XPS）. α-Diimine ligand 1b, bis[N,N′-（2,6- dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2b, {bis[N,N′-（2,6-dimethyl- phenyl）imino]-2,3-butanediylidene}dibromonickel were also synthesized and characterized for comparison. The pre-catalyst 2a with sterically bulky, electron-donating group tert-butyl, activated by diethylaluminum chloride （DEAC） and tested in the polymerization of ethylene, was very highly active[2.01×107 g PE/（mol Ni？h？0.1 MPa）] and led to a very highly branched polyethylene（ca. 35―103 branches/1000 C）. The state of the polyethylene obtained varied from plastic, elastomer polymers to the oil-like hyperbranched polymers.展开更多
The immobilized nickel(II) on the organic-inorganic hybrid material was prepared and used as an effective catalyst for the Biginelli reaction.In the presence of the immobilized nickel catalyst,aromatic aldehydes react...The immobilized nickel(II) on the organic-inorganic hybrid material was prepared and used as an effective catalyst for the Biginelli reaction.In the presence of the immobilized nickel catalyst,aromatic aldehydes reacted with ethyl acetoacetate and urea (or thiourea) smoothly to generate the corresponding Biginelli products in good to excellent yields without using any additive.The work-up procedure is very simple and practical.Furthermore,the silica-supported nickel(II) could be recovered and recycled for six consecutive trials without significant loss of its catalytic activity.展开更多
2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in me...2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in methanol gave mononuclear complex [Ni(bpt)2]· (ClO4)2·H2O and ternary complex [Zn(mpt)2(dmp)](ClO4)2 respectively, where mpt (2,4-dimethoxy-6-(3,5-dimethyl- pyrazol-1-yl)-1,3,5-triazine) and dmp(3,5-dimethylpyrazole) are the alcoholysis products of bpt in the presence of Zn2+ ion. A possible mechanism for this catalytic reaction was proposed. X-ray crystal structure for ligand bpt, Ni and Zn complexes are reported. The protonated form of the ligand bpt crystallizes as its perchlorate salt including one molecule of water, [Hbpt·H2O·ClO4]. The proton is located on one pyrazole N-atom. [Hbpt·H2O·ClO4], in which [Hbpt]+ is in cis-cis conformation, are packed in slipped stacks of approximately parallel layers. The Π -Π overlap interactions between the non-protonized pyrazoles of the adjacent layers give a zigzag arrangement of the planar aromatic [Hbpt]+ molecules. In [Ni(bpt)2](ClO4)2·H2O, bpt are meridionally three-coordinated with Ni2+. The coordination sphere around Ni2+ is a slightly distorted square bipyramid, where four pyrazole nitrogen atoms occupy the basal positions and two triazine nitrogen atoms the apical one. In [Zn(mpt)2(dmp)](ClO4)2, the Zn atom is coordinated with a pair of bidentate mpt ligands and one monodentate dmp ligand, forming a distorted trigonal bipyramid, where the two triazine nitrogen atoms of mpt and one nitrogen atom of dmp occupy the basal positions, and the two pyrazole nitrogen atoms of mpt the apical one.展开更多
The title complexes [M（ImH）4（tfbdc）（H2O）] （1： M = Co; 2： M = Ni） （ImH = imidazole, tfbdc = 2,3,5,6-tetrafluoroterephthalate） were synthesized by the reaction of M（OAc）2·4H2O, H2ffbdc and ImH in wate...The title complexes [M（ImH）4（tfbdc）（H2O）] （1： M = Co; 2： M = Ni） （ImH = imidazole, tfbdc = 2,3,5,6-tetrafluoroterephthalate） were synthesized by the reaction of M（OAc）2·4H2O, H2ffbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X-ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure： monoclinic, P2 1/c, Z=4. M（II） ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc2- and four nitrogen atoms from ImHs. They are discrete zero-dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M（II） between M（III） in electrolysis is a quasi-reversible process.展开更多
The reactions of transition metal salts with taurine 5-chlorosalicylaldelyde Schiff base gave two complexes [Ni(TCSSB)(H2O)3]旽2O (1) and [Cu(TCSSB)(H2O)2]2昜Cu(TCSSB)2]?H2O (2) (TCSSB=taurine-5-chlorosali- cylaldelyd...The reactions of transition metal salts with taurine 5-chlorosalicylaldelyde Schiff base gave two complexes [Ni(TCSSB)(H2O)3]旽2O (1) and [Cu(TCSSB)(H2O)2]2昜Cu(TCSSB)2]?H2O (2) (TCSSB=taurine-5-chlorosali- cylaldelyde Schiff base), which were characterized by elemental analysis and X-ray diffraction analysis. The com-plex 1 crystallized in monoclinic system with space group P2 1/c, and a=1.4816(2) nm, b=1.3953(2) nm, c=0.7466(1) nm, =100.499(3), V=1.5176(4) nm3, Z=4, and an infinite 3-D network structure was formed by hy-drogen bonds among sulfo group, crystal water and coordinated water. Complex 2 crystallized in triclinic system with space group Pī, with the cell parameters: a=0.6413(2) nm, b=1.4596(3) nm, c=1.6188(4) nm, =102.473(5), 猓?8.979(4), =101.739, V=1.4165(6) nm3, Z=1. The coordination environment between Cu(1) and Cu(2) is different. Cu(1) is slightly distorted square pyramidal while Cu(2) is distorted square-plane. The com-plex 1 is mononuclear while the complex 2 is made up of two coordinated subunits, namely [Cu(TCSSB)2] and [Cu(TCSSB)(H2O)2]2. Besides that the TG-DTG of the complex 1 was analyzed, the thermal decomposition reac-tion of the complex was studied under a non-isothermal condition by TG-DTG. The TG and DTG curves indicate that the complex was decomposed in three stages: [Ni(TCSSB)(H2O)3]旽2Oo260104 CHO--→ Ni(TCSSB)(H2O)3o2110155 C3HO--→ Ni(TCSSB)o425610 CTCSSB--→ NiO展开更多
A new complex, [Ni3（L）2（BTA）2]·2H2O （1, L = 1,4-di（1H-imidazol-4-yl）benzene, H3BTA = benzene-1,3,5-triacetic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, ...A new complex, [Ni3（L）2（BTA）2]·2H2O （1, L = 1,4-di（1H-imidazol-4-yl）benzene, H3BTA = benzene-1,3,5-triacetic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, TG and PXRD. The complex crystallizes in monoclinic, space group P1 with a = 9.0303（12）, b = 10.0796（13）, c = 12.7966（17） A, a = 99.268（2）, β= 94.490（2）, y = 103.722（3）°, V = 1108.5（3） A3, Z = 2, C48HasNsO14Ni3, Mr= 1126.99, Dc = 1.688 g/cm3, p = 1.344 mm1, S = 1.001, F（000） = 578, the final R = 0.0389 and wR = 0.0895 for 3083 observed reflections （I 〉 2σ（I））. In the title complex, the flexible BTA3- ligands utilize oxygen atoms of carboxylate groups to coordinate with Ni（II） ions to form two-dimensional double-layer networks which are further pillared into a three-dimension framework via the rigid ditopic ligand L. Topological analysis revealed that complex 1 is a typical （3,8）-connected tfz-d 3D network based on the trinuclear [Ni3（CO2）6N4] subunits.展开更多
The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 11...The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 116.75(3)°, V = 1545.7(5) ?, Z = 4, Mr = 380.04, F(000) = 784, Dc = 1.633 g/cm3 and μ(MoKα) = 1.279 mm–1. The structure was refined to R = 0.0472 and wR = 0.0893 for 2571 observed reflections with I > 2σ(I). The absolute structure Flack parameter X is 0.01(2). In this crystal structure, strong face-to-face π-π stacking interactions between adjacent molecules lead to a one-dimensional chain structure.展开更多
The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spe...The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.展开更多
The title compound, [Ni(acac)2(Im)2] (acac = acetylacetone), has been obtained by the reaction of Ni(acac)2 with imidazole ligand in the ethanol solvent. The blue crystal is of triclinic, space group Pi with a = 7.472...The title compound, [Ni(acac)2(Im)2] (acac = acetylacetone), has been obtained by the reaction of Ni(acac)2 with imidazole ligand in the ethanol solvent. The blue crystal is of triclinic, space group Pi with a = 7.472(2), b = 9.456(2), c = 13.823(3) ? a = 85.55(3), = 89.03(3), ? = 80.63(3)o, C16H22N4NiO4, Mr = 393.09, V = 960.7(3) 3, Z = 2, Dc = 1.359 g/cm3, F(000) = 412, = 1.036 mm-1, R = 0.0549 and wR = 0.1615. The crystal structure consists of two disconnected structural units. Each Ni atom coordinated by two N atoms from two imidazole ligands and four O atoms from two acetylactone ligands adopts a slightly distorted octahedron. The structure characterization was performed by means of IR, UV, TG, elemental analysis and single-crystal X-ray analysis. The thermal gravity (TG) data indicate that thermal decomposition of the title compound takes place in two steps, and the residue is NiO.展开更多
Nickel(II) reacts with 2-acetylpyridine-4-methyl-3-thiosemicarbazone (APMT) and forms a yellow colored complex, which was extracted into n-hexanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance v...Nickel(II) reacts with 2-acetylpyridine-4-methyl-3-thiosemicarbazone (APMT) and forms a yellow colored complex, which was extracted into n-hexanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-APMT complex was measured at different intervals of time at 375 nm to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72 hrs. The system obeyed Beer’s law in the concentration range of 0.235 - 2.43 μg·ml–1 of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell’s sensitivity of the extracted species were found to be 2.16 × 104 L mol–1 ·cm–1 and 0.003 μg·cm–2 at 375 nm, respectively. Hence a detailed study of the extraction of nickel(II) with APMT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.展开更多
A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. I...A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. It crystallizes in triclinic, space group P1 with a = 11.861(2), b = 18.384(4), c = 19.746(3) ?, α = 107.68(1), β = 105.94(1), γ = 103.41(2)°, V = 3703.6(11) ?3, Mr = 1745.66, Z = 2, Dc =1.565 g/cm3, μ = 0.989 mm-1, F(000) = 1791, R = 0.0643 and wR = 0.1611. The complex contains two cations, binuclear [Ni2(L-Asp)(Phen)3(H2O)]2+ and mononu- clear [Ni(Phen)2(H2O)2]2+. All the nickel ions in the complex are six-coordinated with a distorted octahedral geometry, but the coordination environments for them are different. There exist hydrogen bonds and π-π stacking interactions in the complex.展开更多
Two tri-n-butylphosphme-participated ( PBu3n) nickel (Ⅱ) complexes of 2-mercaptophenol(H2mp),i.e,Ni2Ru(mp)3(Hmp)(PBu3n)3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear "synthon",[...Two tri-n-butylphosphme-participated ( PBu3n) nickel (Ⅱ) complexes of 2-mercaptophenol(H2mp),i.e,Ni2Ru(mp)3(Hmp)(PBu3n)3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear "synthon",[HNEt3] [Ni(mp) (Hmp) (PBu3n)] 1 were synthesized and characterized by X-crystallography and 1H NMR,FAB-MS and cyclic valtammogram measurements.The nickel(Ⅱ) center in 1 has a square-planar geometry For 3,the ruthenium(Ⅲ) atom is in a distorted octahedral environment and the two mckel(Ⅱ) atoms exhibit square-planar and rare triangle-planar geometries,respectively.The Ni (1)-Ru-Ni(2 ) arrangement is severely asymmetric with the distances 0.254 and 0.394 nm,respectively,for Ni(1)-Ru and Ni(2)-Ru.The structural regularities of relevant complexes are summarized in relation to the structural as well as spectra data.展开更多
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.
基金supported by the International Technology Cooperation Project of Science and Technology Department of Henan Province(No.124300510050)
文摘A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638（3）, b = 10.2319（3）, c = 13.2463（4） ？, α = 80.1710（10）, β = 83.671（2）, γ = 70.3790（10）o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85（6） ？3, Dc = 1.746 g/cm3, F（000） = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ（I）. In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.
文摘A fluorescent Ni（II） complex 1, [Ni（OH-H2Bdc）（Bibimp）]n·nH2O, constructed with 5-hydroxyisophthalic acid（OH-H2Bdc） and 2,6-bis（2-benzimidazolyl）pyridine）（Bibimp） has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a = 10.187（2）, b = 10.273（2）, c = 13.401（3）A, α = 69.65（3）, β = 69.66（3）, γ = 70.61（3）°, V = 1196.8（4） A3, and Z = 2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C–H…O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.
基金Supported by the National Natural Science Foundation of China(No.20964003)
文摘A new α-diimine ligand 1a, bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2a, {bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene}dibromo- nickel were successfully synthesized, and characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscope（FTIR）, elemental analysis and X-ray photoelectron spectroscopy（XPS）. α-Diimine ligand 1b, bis[N,N′-（2,6- dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2b, {bis[N,N′-（2,6-dimethyl- phenyl）imino]-2,3-butanediylidene}dibromonickel were also synthesized and characterized for comparison. The pre-catalyst 2a with sterically bulky, electron-donating group tert-butyl, activated by diethylaluminum chloride （DEAC） and tested in the polymerization of ethylene, was very highly active[2.01×107 g PE/（mol Ni？h？0.1 MPa）] and led to a very highly branched polyethylene（ca. 35―103 branches/1000 C）. The state of the polyethylene obtained varied from plastic, elastomer polymers to the oil-like hyperbranched polymers.
基金financial support by the National Natural Science Foundation of China (20972057, 20772043)the Excellent Scientist Foundation of Anhui Province, China (04046080)the Natural Science Foundation of Anhui Province's Higher Education, China (KJ2009B212Z)
文摘The immobilized nickel(II) on the organic-inorganic hybrid material was prepared and used as an effective catalyst for the Biginelli reaction.In the presence of the immobilized nickel catalyst,aromatic aldehydes reacted with ethyl acetoacetate and urea (or thiourea) smoothly to generate the corresponding Biginelli products in good to excellent yields without using any additive.The work-up procedure is very simple and practical.Furthermore,the silica-supported nickel(II) could be recovered and recycled for six consecutive trials without significant loss of its catalytic activity.
基金the National Natural Science Foundation of China (Grant No. 29671034) and Natural Science Foundation of Guangdong Province (Grant Nos. 990128,974174).
文摘2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(ClO4)2·6H2O and Zn(ClO4)2·6H2O in methanol gave mononuclear complex [Ni(bpt)2]· (ClO4)2·H2O and ternary complex [Zn(mpt)2(dmp)](ClO4)2 respectively, where mpt (2,4-dimethoxy-6-(3,5-dimethyl- pyrazol-1-yl)-1,3,5-triazine) and dmp(3,5-dimethylpyrazole) are the alcoholysis products of bpt in the presence of Zn2+ ion. A possible mechanism for this catalytic reaction was proposed. X-ray crystal structure for ligand bpt, Ni and Zn complexes are reported. The protonated form of the ligand bpt crystallizes as its perchlorate salt including one molecule of water, [Hbpt·H2O·ClO4]. The proton is located on one pyrazole N-atom. [Hbpt·H2O·ClO4], in which [Hbpt]+ is in cis-cis conformation, are packed in slipped stacks of approximately parallel layers. The Π -Π overlap interactions between the non-protonized pyrazoles of the adjacent layers give a zigzag arrangement of the planar aromatic [Hbpt]+ molecules. In [Ni(bpt)2](ClO4)2·H2O, bpt are meridionally three-coordinated with Ni2+. The coordination sphere around Ni2+ is a slightly distorted square bipyramid, where four pyrazole nitrogen atoms occupy the basal positions and two triazine nitrogen atoms the apical one. In [Zn(mpt)2(dmp)](ClO4)2, the Zn atom is coordinated with a pair of bidentate mpt ligands and one monodentate dmp ligand, forming a distorted trigonal bipyramid, where the two triazine nitrogen atoms of mpt and one nitrogen atom of dmp occupy the basal positions, and the two pyrazole nitrogen atoms of mpt the apical one.
基金Acknowledgement This work was supported by the National Natural Science Foundation of China （Nos. 20671045, 20971060, 21101018） and the Natural Science Foundation of State Key Laboratory of Coordination Chemistry.
文摘The title complexes [M（ImH）4（tfbdc）（H2O）] （1： M = Co; 2： M = Ni） （ImH = imidazole, tfbdc = 2,3,5,6-tetrafluoroterephthalate） were synthesized by the reaction of M（OAc）2·4H2O, H2ffbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X-ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure： monoclinic, P2 1/c, Z=4. M（II） ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc2- and four nitrogen atoms from ImHs. They are discrete zero-dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M（II） between M（III） in electrolysis is a quasi-reversible process.
基金Project supported by the Natural Science Foundation of Guangxi Province (No. 0339034) and the Science Research Foundation of Guangxi Univer-sities.
文摘The reactions of transition metal salts with taurine 5-chlorosalicylaldelyde Schiff base gave two complexes [Ni(TCSSB)(H2O)3]旽2O (1) and [Cu(TCSSB)(H2O)2]2昜Cu(TCSSB)2]?H2O (2) (TCSSB=taurine-5-chlorosali- cylaldelyde Schiff base), which were characterized by elemental analysis and X-ray diffraction analysis. The com-plex 1 crystallized in monoclinic system with space group P2 1/c, and a=1.4816(2) nm, b=1.3953(2) nm, c=0.7466(1) nm, =100.499(3), V=1.5176(4) nm3, Z=4, and an infinite 3-D network structure was formed by hy-drogen bonds among sulfo group, crystal water and coordinated water. Complex 2 crystallized in triclinic system with space group Pī, with the cell parameters: a=0.6413(2) nm, b=1.4596(3) nm, c=1.6188(4) nm, =102.473(5), 猓?8.979(4), =101.739, V=1.4165(6) nm3, Z=1. The coordination environment between Cu(1) and Cu(2) is different. Cu(1) is slightly distorted square pyramidal while Cu(2) is distorted square-plane. The com-plex 1 is mononuclear while the complex 2 is made up of two coordinated subunits, namely [Cu(TCSSB)2] and [Cu(TCSSB)(H2O)2]2. Besides that the TG-DTG of the complex 1 was analyzed, the thermal decomposition reac-tion of the complex was studied under a non-isothermal condition by TG-DTG. The TG and DTG curves indicate that the complex was decomposed in three stages: [Ni(TCSSB)(H2O)3]旽2Oo260104 CHO--→ Ni(TCSSB)(H2O)3o2110155 C3HO--→ Ni(TCSSB)o425610 CTCSSB--→ NiO
基金supported by the National Natural Science Foundation of China(No.21171040)the Natural Science Foundation of Anhui Provincial Education Commission(No.KJ2011B128 and KJ2011B123)
文摘A new complex, [Ni3（L）2（BTA）2]·2H2O （1, L = 1,4-di（1H-imidazol-4-yl）benzene, H3BTA = benzene-1,3,5-triacetic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, TG and PXRD. The complex crystallizes in monoclinic, space group P1 with a = 9.0303（12）, b = 10.0796（13）, c = 12.7966（17） A, a = 99.268（2）, β= 94.490（2）, y = 103.722（3）°, V = 1108.5（3） A3, Z = 2, C48HasNsO14Ni3, Mr= 1126.99, Dc = 1.688 g/cm3, p = 1.344 mm1, S = 1.001, F（000） = 578, the final R = 0.0389 and wR = 0.0895 for 3083 observed reflections （I 〉 2σ（I））. In the title complex, the flexible BTA3- ligands utilize oxygen atoms of carboxylate groups to coordinate with Ni（II） ions to form two-dimensional double-layer networks which are further pillared into a three-dimension framework via the rigid ditopic ligand L. Topological analysis revealed that complex 1 is a typical （3,8）-connected tfz-d 3D network based on the trinuclear [Ni3（CO2）6N4] subunits.
基金The project was supported by the Education Department of Zhejiang Province (20030710)
文摘The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 116.75(3)°, V = 1545.7(5) ?, Z = 4, Mr = 380.04, F(000) = 784, Dc = 1.633 g/cm3 and μ(MoKα) = 1.279 mm–1. The structure was refined to R = 0.0472 and wR = 0.0893 for 2571 observed reflections with I > 2σ(I). The absolute structure Flack parameter X is 0.01(2). In this crystal structure, strong face-to-face π-π stacking interactions between adjacent molecules lead to a one-dimensional chain structure.
基金supported by the National Natural Science Foundation of China (No. 20671016)Education Committee of Jilin Province "11th Five-year Plan" Natural Science Foundation (No. 2006124)
文摘The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.
基金This work was supported bythe Natural Science Foundation of Shandong Province (No. Y2002B06) and Science Research Foundation of Qingdao University of Science and Technology (No. 03Z08)
文摘The title compound, [Ni(acac)2(Im)2] (acac = acetylacetone), has been obtained by the reaction of Ni(acac)2 with imidazole ligand in the ethanol solvent. The blue crystal is of triclinic, space group Pi with a = 7.472(2), b = 9.456(2), c = 13.823(3) ? a = 85.55(3), = 89.03(3), ? = 80.63(3)o, C16H22N4NiO4, Mr = 393.09, V = 960.7(3) 3, Z = 2, Dc = 1.359 g/cm3, F(000) = 412, = 1.036 mm-1, R = 0.0549 and wR = 0.1615. The crystal structure consists of two disconnected structural units. Each Ni atom coordinated by two N atoms from two imidazole ligands and four O atoms from two acetylactone ligands adopts a slightly distorted octahedron. The structure characterization was performed by means of IR, UV, TG, elemental analysis and single-crystal X-ray analysis. The thermal gravity (TG) data indicate that thermal decomposition of the title compound takes place in two steps, and the residue is NiO.
文摘Nickel(II) reacts with 2-acetylpyridine-4-methyl-3-thiosemicarbazone (APMT) and forms a yellow colored complex, which was extracted into n-hexanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-APMT complex was measured at different intervals of time at 375 nm to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72 hrs. The system obeyed Beer’s law in the concentration range of 0.235 - 2.43 μg·ml–1 of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell’s sensitivity of the extracted species were found to be 2.16 × 104 L mol–1 ·cm–1 and 0.003 μg·cm–2 at 375 nm, respectively. Hence a detailed study of the extraction of nickel(II) with APMT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.
基金This work was supported by the Natural Science Foundation of Guangxi Province (No. 9912044)
文摘A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. It crystallizes in triclinic, space group P1 with a = 11.861(2), b = 18.384(4), c = 19.746(3) ?, α = 107.68(1), β = 105.94(1), γ = 103.41(2)°, V = 3703.6(11) ?3, Mr = 1745.66, Z = 2, Dc =1.565 g/cm3, μ = 0.989 mm-1, F(000) = 1791, R = 0.0643 and wR = 0.1611. The complex contains two cations, binuclear [Ni2(L-Asp)(Phen)3(H2O)]2+ and mononu- clear [Ni(Phen)2(H2O)2]2+. All the nickel ions in the complex are six-coordinated with a distorted octahedral geometry, but the coordination environments for them are different. There exist hydrogen bonds and π-π stacking interactions in the complex.
文摘Two tri-n-butylphosphme-participated ( PBu3n) nickel (Ⅱ) complexes of 2-mercaptophenol(H2mp),i.e,Ni2Ru(mp)3(Hmp)(PBu3n)3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear "synthon",[HNEt3] [Ni(mp) (Hmp) (PBu3n)] 1 were synthesized and characterized by X-crystallography and 1H NMR,FAB-MS and cyclic valtammogram measurements.The nickel(Ⅱ) center in 1 has a square-planar geometry For 3,the ruthenium(Ⅲ) atom is in a distorted octahedral environment and the two mckel(Ⅱ) atoms exhibit square-planar and rare triangle-planar geometries,respectively.The Ni (1)-Ru-Ni(2 ) arrangement is severely asymmetric with the distances 0.254 and 0.394 nm,respectively,for Ni(1)-Ru and Ni(2)-Ru.The structural regularities of relevant complexes are summarized in relation to the structural as well as spectra data.
