Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex...Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex/alcohol molar ratio to optimize reaction conditions and to evaluate the catalytic efficiency of new cobalt Schiff base complexes.Under obtained optimum conditions,various alcohols were oxidized to corresponding aldehydes and ketones.展开更多
Two cobalt（Ⅱ） complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL^1 and CoL^2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester （PNPP）. The analys...Two cobalt（Ⅱ） complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL^1 and CoL^2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester （PNPP）. The analysis of specific absorption spectra of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Co（Ⅱ） complexes, have been formed in reaction processes of the PNPP catalytic hydrolysis. The mechanism of PNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis, has been established based on the mechanism proposed. The acid effect of buffer solution, structural effect of the complexes, and effect of temperature on the rate of PNPP hydrolysis catalyzed by the complexes have been also discussed.展开更多
Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido...Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.展开更多
The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous met...The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.展开更多
Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring...Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring cobalt(Ⅱ)ions are linked together by one bridging diaphonic acid group,forming an asymmetric dinuclear structure.1 crystallizes in triclinic,space group P1 with a=9.825(6),b=13.007(8),c=19.586(1)A,α=80.773(1)o,β=77.065(1)o,γ=85.902(1)o,Mr=431.4,V=2406.5(3)A^3,Dc=1.48 g/cm^3,Z=2,μ(Mo Kα)=0.767 mm-1,F(000)=1112,the final R=0.0379 and wR=0.0862.The central cobalt(Ⅱ)ions in 1 and 2 are coordinated with six atoms,forming distorted octahedral coordination geometry.The fluorescence and thermal stability properties of 1 and 2 are also reported.展开更多
Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane ...Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.展开更多
Three novel Schiff base cobalt（Ⅱ） complexes containing benzoaza-15-crown-5, CoL^1, CoL^2 and CoL^3 were synthesized and characterized, and these complexes were used in catalytic hydrolysis of carboxylic ester （PNP...Three novel Schiff base cobalt（Ⅱ） complexes containing benzoaza-15-crown-5, CoL^1, CoL^2 and CoL^3 were synthesized and characterized, and these complexes were used in catalytic hydrolysis of carboxylic ester （PNPP, p-nitrophenyl picolinate） as mimic hydrolytic metalloenzyme. The analysis of specific absorption spectra of the hydrolytic reaction systems indicated that the catalytic hydrolysis involved the key intermediates formed by PNPP with cobalt（Ⅱ） complexes. The CoL^3 bearing the electron withdrawing group shows better catalytic activity due to its stabilization effect on active species MLS^-. The catalytic mechanism of PNPP hydrolysis was also proposed. The kinetic parameter of PNPP catalytic hydrolysis has been calculated and the activation energy for the catalytic hydrolysis is 43.69, 39.76 and 35.44 kJ·mol^-1, respectively.展开更多
Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in...Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490（2）,b = 19.210（7）,c = 7.813（3） ,β = 92.716（5）o,V = 972.9（6） 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F（000） = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ（I）.Complex 2 is isomorphous with 1,with a = 6.478（2）,b = 19.052（7）,c = 7.742（3） ,β = 92.690（4）o,V = 954.6（6） 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F（000） = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ（I）.In the compounds,the mononuclear [M（L）2（H2O）4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding（or second-sphere coordination） involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol（4·62）2（42·623·83）.展开更多
Introduction The compounds that can take up and release molecular oxygen reversibly is of significance because they can be used as model compounds for the study of the reversible oxygenation mechanisms involved in the...Introduction The compounds that can take up and release molecular oxygen reversibly is of significance because they can be used as model compounds for the study of the reversible oxygenation mechanisms involved in the very complex natural oxygen carriers, e.g., the hemoglobins and hemocyanins, and as the means of separating molecular oxygen from the air. The dioxygen carriers extensively studied are the Cobalt展开更多
This paper reports mainly the preparation of silica supported acetylacetone ligands and their cobalt complexes, the characterization of their chemical structure, and the evaluation of their catalytic activity in the r...This paper reports mainly the preparation of silica supported acetylacetone ligands and their cobalt complexes, the characterization of their chemical structure, and the evaluation of their catalytic activity in the reaction for the preparation of ethers directly from alkanols and benzyl chloride. The results indicate that those silica supported β-diketone cobalt complexes (SACO) not only can simplify the reaction procedure of the ether preparation but also show a much higher catalytic activity in comparison with other homogeneous catalysts. In addition, SACO can be recovered and reused although their catalytic activity descend gradually as a result of the decrease in their cobalt content.展开更多
A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental an...A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental analyses, molar conductance, 1H NMR DTA, TG, IR and UV spectroscopy. In these complexes the ligand is coordinated to the metal through its phenolic oxygen, carboxyl oxygen, imino nitrogen and amide nitrogen. All complexes are non-electrolytes and four coordinated with 1:1(metal; ligand) stoichiometry. The probable structure of the complexes is suggested展开更多
Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol ...Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.展开更多
Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in ...Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146（2）, b = 9.4864（10）, c = 13.9261（15）A, β = 102.898（2）°, V = 2980.6（5） ？3, Z = 4, Dc = 1.367 g/cm3, F（000） = 1284 and μ = 0.616 mm^-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807（11）, b = 13.118（10）, c = 16.663（13） A, β = 111.237（14）°, V = 3017（4） A^3, Z = 4, Dc = 1.342 g/cm^3, F（000） = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H…π hydrogen bonds and C–H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.展开更多
The oxygenation constants and thermodynamic parameter （△H°, △S°） of a series of novel Co （Ⅱ） complexes with phenol ether bridged dihydroxamic acids CoL^1-CoL^6 were measured, their catalytic performan...The oxygenation constants and thermodynamic parameter （△H°, △S°） of a series of novel Co （Ⅱ） complexes with phenol ether bridged dihydroxamic acids CoL^1-CoL^6 were measured, their catalytic performance in oxidation of p-xylene to p-toluic acid （PTA） were examined. The modulation of O2-binding capabilities and catalytic oxidation activities by X （X = Cl, OCH3） and Y （Y = H, CH3, Cl） groups bonded to the aromatic rings of the Co （Ⅱ） complexes were investigated.展开更多
Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized...Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.展开更多
Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hy...Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.展开更多
Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terp...Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
A new metal-organic complex Co2（cbba）4（phen）2（μ2-OH2）（H2cbba=2-（4＇-chlorine-benzoyl）benzoic acid,phen=1,10-phenanthroline） 1 has been hydrothermally synthesized and struc-turally characterized by single-cr...A new metal-organic complex Co2（cbba）4（phen）2（μ2-OH2）（H2cbba=2-（4＇-chlorine-benzoyl）benzoic acid,phen=1,10-phenanthroline） 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.7659（7）,b=17.1856（11）,c=19.2022（13）,α=83.8120（10）,β=84.9930（10）,γ=87.2070（10）°,V=3515.8（4）3,C80H50Cl4Co2N4O13,Mr=1534.90,Dc=1.450 g/cm3,μ（MoKα）=0.693 mm-1,F（000）=1568,Z=2,the final R=0.0490 and wR=0.1092 for 8216 observed reflections（Ⅰ 〉2σ（Ⅰ））.In the crystal structure,the cobalt atom is six-coordinated with three carboxylate oxygen atoms from three different cbba ligands,one oxygen atom from coordinated water molecule and two nitrogen atoms from phen ligand,showing a distorted octahedral geometry.Furthermore,it exhibits a 3D supramolecular network through π-π and hydrogen bonding interactions.展开更多
A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and s...A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.展开更多
文摘Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex/alcohol molar ratio to optimize reaction conditions and to evaluate the catalytic efficiency of new cobalt Schiff base complexes.Under obtained optimum conditions,various alcohols were oxidized to corresponding aldehydes and ketones.
基金Project supported by the Educational Department of Sichuan Government （No.2005D007） and the National Natural Science Foundation of China （Nos.20173038, 20107004）.
文摘Two cobalt（Ⅱ） complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL^1 and CoL^2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester （PNPP）. The analysis of specific absorption spectra of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Co（Ⅱ） complexes, have been formed in reaction processes of the PNPP catalytic hydrolysis. The mechanism of PNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis, has been established based on the mechanism proposed. The acid effect of buffer solution, structural effect of the complexes, and effect of temperature on the rate of PNPP hydrolysis catalyzed by the complexes have been also discussed.
基金Supported by the National Natural Science Foundation of China (No. 60978059)Program for New Century Excellent Talents in University (NCET-10-0176)the Natural Science Foundation of Jilin Province (No. 20090527)
文摘Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.
文摘The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
基金Supported by Hunan Provincial Natural Science Foundation of China(2019JJ60021)the Scientific Research Found of Hunan Provincial Education Department of China(17A049,17C0226)Industry and Research Key Project of Hengyang City(2018KJ016)
文摘Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring cobalt(Ⅱ)ions are linked together by one bridging diaphonic acid group,forming an asymmetric dinuclear structure.1 crystallizes in triclinic,space group P1 with a=9.825(6),b=13.007(8),c=19.586(1)A,α=80.773(1)o,β=77.065(1)o,γ=85.902(1)o,Mr=431.4,V=2406.5(3)A^3,Dc=1.48 g/cm^3,Z=2,μ(Mo Kα)=0.767 mm-1,F(000)=1112,the final R=0.0379 and wR=0.0862.The central cobalt(Ⅱ)ions in 1 and 2 are coordinated with six atoms,forming distorted octahedral coordination geometry.The fluorescence and thermal stability properties of 1 and 2 are also reported.
基金supported by the National Natural Science Foundation of China(No.21571093)the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.14HASTIT017)+1 种基金the Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.14IRTSTHN008)the Foundation of Education Committee of Henan Province(No.142300410301)
文摘Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.
基金Project supported by the Educational Department of Sichuan Government （No. 2005D007） and the National Natural Science Foundation of China （Nos. 20173038, 20107004）.
文摘Three novel Schiff base cobalt（Ⅱ） complexes containing benzoaza-15-crown-5, CoL^1, CoL^2 and CoL^3 were synthesized and characterized, and these complexes were used in catalytic hydrolysis of carboxylic ester （PNPP, p-nitrophenyl picolinate） as mimic hydrolytic metalloenzyme. The analysis of specific absorption spectra of the hydrolytic reaction systems indicated that the catalytic hydrolysis involved the key intermediates formed by PNPP with cobalt（Ⅱ） complexes. The CoL^3 bearing the electron withdrawing group shows better catalytic activity due to its stabilization effect on active species MLS^-. The catalytic mechanism of PNPP hydrolysis was also proposed. The kinetic parameter of PNPP catalytic hydrolysis has been calculated and the activation energy for the catalytic hydrolysis is 43.69, 39.76 and 35.44 kJ·mol^-1, respectively.
基金Supported by NNSFC (20771038)Shanghai Leading Academic Discipline Project (B409)
文摘Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490（2）,b = 19.210（7）,c = 7.813（3） ,β = 92.716（5）o,V = 972.9（6） 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F（000） = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ（I）.Complex 2 is isomorphous with 1,with a = 6.478（2）,b = 19.052（7）,c = 7.742（3） ,β = 92.690（4）o,V = 954.6（6） 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F（000） = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ（I）.In the compounds,the mononuclear [M（L）2（H2O）4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding（or second-sphere coordination） involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol（4·62）2（42·623·83）.
基金Supported by Shandong University Youth Scientific Foundation
文摘Introduction The compounds that can take up and release molecular oxygen reversibly is of significance because they can be used as model compounds for the study of the reversible oxygenation mechanisms involved in the very complex natural oxygen carriers, e.g., the hemoglobins and hemocyanins, and as the means of separating molecular oxygen from the air. The dioxygen carriers extensively studied are the Cobalt
文摘This paper reports mainly the preparation of silica supported acetylacetone ligands and their cobalt complexes, the characterization of their chemical structure, and the evaluation of their catalytic activity in the reaction for the preparation of ethers directly from alkanols and benzyl chloride. The results indicate that those silica supported β-diketone cobalt complexes (SACO) not only can simplify the reaction procedure of the ether preparation but also show a much higher catalytic activity in comparison with other homogeneous catalysts. In addition, SACO can be recovered and reused although their catalytic activity descend gradually as a result of the decrease in their cobalt content.
文摘A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental analyses, molar conductance, 1H NMR DTA, TG, IR and UV spectroscopy. In these complexes the ligand is coordinated to the metal through its phenolic oxygen, carboxyl oxygen, imino nitrogen and amide nitrogen. All complexes are non-electrolytes and four coordinated with 1:1(metal; ligand) stoichiometry. The probable structure of the complexes is suggested
文摘Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.
基金supported by the National Natural Science Foundation of China(No.21272008)the Natural Science Industry-University-Research Foundation of Suzhou University(2015hx014)
文摘Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146（2）, b = 9.4864（10）, c = 13.9261（15）A, β = 102.898（2）°, V = 2980.6（5） ？3, Z = 4, Dc = 1.367 g/cm3, F（000） = 1284 and μ = 0.616 mm^-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807（11）, b = 13.118（10）, c = 16.663（13） A, β = 111.237（14）°, V = 3017（4） A^3, Z = 4, Dc = 1.342 g/cm^3, F（000） = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H…π hydrogen bonds and C–H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.
基金supported by the National Natural Science Foundation of China(No.2007205).
文摘The oxygenation constants and thermodynamic parameter （△H°, △S°） of a series of novel Co （Ⅱ） complexes with phenol ether bridged dihydroxamic acids CoL^1-CoL^6 were measured, their catalytic performance in oxidation of p-xylene to p-toluic acid （PTA） were examined. The modulation of O2-binding capabilities and catalytic oxidation activities by X （X = Cl, OCH3） and Y （Y = H, CH3, Cl） groups bonded to the aromatic rings of the Co （Ⅱ） complexes were investigated.
基金supported by the Science and Technology Development Project of Jilin Provincial Science & Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘Two new coordination polymers [Co（oba）（mbix）]2n·nH2O （1） and [Mn（Hoba）2（H2O）2]n （2） （H2oba = 4,4＇-oxydibenzoic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）benzene） have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.
基金supported by the Science and Technology development plan of Jilin Province(2015052006JH)
文摘Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2009. 272)
文摘A new metal-organic complex Co2（cbba）4（phen）2（μ2-OH2）（H2cbba=2-（4＇-chlorine-benzoyl）benzoic acid,phen=1,10-phenanthroline） 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.7659（7）,b=17.1856（11）,c=19.2022（13）,α=83.8120（10）,β=84.9930（10）,γ=87.2070（10）°,V=3515.8（4）3,C80H50Cl4Co2N4O13,Mr=1534.90,Dc=1.450 g/cm3,μ（MoKα）=0.693 mm-1,F（000）=1568,Z=2,the final R=0.0490 and wR=0.1092 for 8216 observed reflections（Ⅰ 〉2σ（Ⅰ））.In the crystal structure,the cobalt atom is six-coordinated with three carboxylate oxygen atoms from three different cbba ligands,one oxygen atom from coordinated water molecule and two nitrogen atoms from phen ligand,showing a distorted octahedral geometry.Furthermore,it exhibits a 3D supramolecular network through π-π and hydrogen bonding interactions.
基金supported by Science and Technology Research Projects of the Education Office of Jilin Province (No. 2007. 213)
文摘A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.
