As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates hav...As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.展开更多
The polymerization kinetics of 4, 4'-biphenyldicarbonitrile and other substituted ben-zonitriles catalyzed by cobaltic acetylacetonate was studied. The structure of polymer ofdifferent substituted benzonitrile was...The polymerization kinetics of 4, 4'-biphenyldicarbonitrile and other substituted ben-zonitriles catalyzed by cobaltic acetylacetonate was studied. The structure of polymer ofdifferent substituted benzonitrile was also determined. It is found that the rate of polymeri-zation and the structure of polymer is greatly affected by the substituent of benzonitriles.展开更多
A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-cry...A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.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
The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex c...The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) ?, β = 91.181(3)o, V = 1457.70(17) ?3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm–1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2σ(I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N–H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face dis- tance of 3.604 ? are found in the packing diagram.展开更多
The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound ...The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.展开更多
Solvent free, highly efficient method has been developed using ecofriendly, heterogeneous reusable cobalt chloride catalyst at ambient reaction conditions for the O-acylation of various alcohols and phenols with acety...Solvent free, highly efficient method has been developed using ecofriendly, heterogeneous reusable cobalt chloride catalyst at ambient reaction conditions for the O-acylation of various alcohols and phenols with acetyl chloride in excellent yield in a short reaction time. The catalyst is recycled several times without loss of catalytic activity.展开更多
A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure...A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.展开更多
A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectr...A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectroscopy, 1H-NMR, elemental analysis, TGA and single crystal X-ray structure determination. X-ray crystal structure analysis shows an octahedral complex with a metal centre coordinated to two ligand molecules through the pyridine nitrogen atoms and four water molecules and containing two nitrate groups as counter ions. The complex crystallizes in the monoclinic crystal system and P2(1)/n space group. The unit cell dimensions are: a = 7.2108(4) Å, b = 16.6020(9) Å, c = 13.0389(6) Å,α = 90°, β = 103.972(4)°, γ = 90°. The molecule is symmetrical about the cobalt centre as observed from the 1H-NMR and 13C-NMR and confirmed by the single crystal X-ray structure of the complex. Thermogravimetric analysis shows two steps decomposition of the complex to leave a metal oxide residue. The title compound is expected to be biologically active as one of the precursors (isoniazid) is a therapeutic agent with well-established clinical applications.展开更多
[Objective]The paper was to synthesize a new structure of metal organic framework,and to provide new materials for plant pathogens testing.[Method]A mixture of 2,6-di(2’,4’-di-carboxylphenyl)pyridine,1,4-bis(1-imida...[Objective]The paper was to synthesize a new structure of metal organic framework,and to provide new materials for plant pathogens testing.[Method]A mixture of 2,6-di(2’,4’-di-carboxylphenyl)pyridine,1,4-bis(1-imidazolyl)benzene,Co(NO_(3))2·6H_(2)O were added to the solution of DMF:H2O=3:3 and heated at 433K for 4 d.[Result]Red crystals of the title compound were obtained(yield 76.3%,based on Co).[Conclusion]The crystal data were obtained as follows:C_(39)H_(24)Co_(2)N_(7)O_(8),monoclinic,P21/c,a=16.222(7)A,b=12.653(5)A,c=17.456(7)A,β=102.386(6)°,V=3500(2)A_(3),Z=4,Rgt(F)=0.0550,wRref(F2)=0.1509,T=293(2)K.展开更多
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th...Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.展开更多
The oxygenation of cobalt (II) hydroxamates (CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined. The effects of X and Y bonded to hydroxamate group on dioxygen affinitie...The oxygenation of cobalt (II) hydroxamates (CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined. The effects of X and Y bonded to hydroxamate group on dioxygen affinities and catalytic oxidation performance were also investigated.展开更多
The self-assembly of a flexible bipyridyl ligand 2,2?-bis(4-pyridylmethyle- neoxy)-1,1?-biphenylene (4,4?-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4?-bpp)2(SCN)2?H2O]n 1 which ...The self-assembly of a flexible bipyridyl ligand 2,2?-bis(4-pyridylmethyle- neoxy)-1,1?-biphenylene (4,4?-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4?-bpp)2(SCN)2?H2O]n 1 which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in monoclinic, space group C2/c with unit cell parameters: a = 13.1888(13), b = 24.230(2), c = 15.4218(17) ?, β = 93.291(6)o, V = 4920.1(8) ?3, Z = 4, C50H42CoN6O5S2, Mr = 929.95, Dc = 1.255 g/cm3, F(000) = 1932 and μ(MoKα) = 0.484 mm-1. The final R and wR are 0.0691 and 0.1670 for 3746 observed reflections with I > 2σ(I). 1 possesses an infinite 1-D polymeric chain structure consisting of the repeated basic square units Co2(μ-4,4?-bpp)2, where the Co(II) center acts as the joint of the square ring. The Co(II) center is coordinated in a slightly distorted octahedral geometry with four nitrogen atoms from four different 4,4?-bpp ligands in the equatorial plane and two trans thiocyanate ligands occupying the axial positions, preventing the formation of an extended framework.展开更多
基金financial support from the National Key Research and Development Program of China(2020YFA0710202)the National Natural Science Foundation of China(21978043,U1662130)+1 种基金Inner Mongolia University of Technology Scientific Research Initial Funding(DC2300001240)Talent Introduction Support Project of Inner Mongolia(DC2300001426).
文摘As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.
文摘The polymerization kinetics of 4, 4'-biphenyldicarbonitrile and other substituted ben-zonitriles catalyzed by cobaltic acetylacetonate was studied. The structure of polymer ofdifferent substituted benzonitrile was also determined. It is found that the rate of polymeri-zation and the structure of polymer is greatly affected by the substituent of benzonitriles.
基金This work was supported by the National Natural Science Foundation of China (No. 20101003), Natural Science Foundation of Heilongjiang Province (No. B0007) and the Scientific Fund of Remarkable Teachers of Heilongjiang Province (1054G036)
文摘A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.
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.
基金Supported by the National Natural Science Foundation of China (20325106 20333070)and the "One-hundred Talent" Project from the Chinese Academy of Sciences
文摘The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) ?, β = 91.181(3)o, V = 1457.70(17) ?3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm–1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2σ(I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N–H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face dis- tance of 3.604 ? are found in the packing diagram.
文摘The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.
文摘Solvent free, highly efficient method has been developed using ecofriendly, heterogeneous reusable cobalt chloride catalyst at ambient reaction conditions for the O-acylation of various alcohols and phenols with acetyl chloride in excellent yield in a short reaction time. The catalyst is recycled several times without loss of catalytic activity.
文摘A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.
文摘A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectroscopy, 1H-NMR, elemental analysis, TGA and single crystal X-ray structure determination. X-ray crystal structure analysis shows an octahedral complex with a metal centre coordinated to two ligand molecules through the pyridine nitrogen atoms and four water molecules and containing two nitrate groups as counter ions. The complex crystallizes in the monoclinic crystal system and P2(1)/n space group. The unit cell dimensions are: a = 7.2108(4) Å, b = 16.6020(9) Å, c = 13.0389(6) Å,α = 90°, β = 103.972(4)°, γ = 90°. The molecule is symmetrical about the cobalt centre as observed from the 1H-NMR and 13C-NMR and confirmed by the single crystal X-ray structure of the complex. Thermogravimetric analysis shows two steps decomposition of the complex to leave a metal oxide residue. The title compound is expected to be biologically active as one of the precursors (isoniazid) is a therapeutic agent with well-established clinical applications.
基金Hainan Major Research Found of Science and Technology(ZDKJ201817).
文摘[Objective]The paper was to synthesize a new structure of metal organic framework,and to provide new materials for plant pathogens testing.[Method]A mixture of 2,6-di(2’,4’-di-carboxylphenyl)pyridine,1,4-bis(1-imidazolyl)benzene,Co(NO_(3))2·6H_(2)O were added to the solution of DMF:H2O=3:3 and heated at 433K for 4 d.[Result]Red crystals of the title compound were obtained(yield 76.3%,based on Co).[Conclusion]The crystal data were obtained as follows:C_(39)H_(24)Co_(2)N_(7)O_(8),monoclinic,P21/c,a=16.222(7)A,b=12.653(5)A,c=17.456(7)A,β=102.386(6)°,V=3500(2)A_(3),Z=4,Rgt(F)=0.0550,wRref(F2)=0.1509,T=293(2)K.
文摘Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.
基金This work is supported by the National Natural Science Foundation of China(Grant No.2007205).
文摘The oxygenation of cobalt (II) hydroxamates (CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined. The effects of X and Y bonded to hydroxamate group on dioxygen affinities and catalytic oxidation performance were also investigated.
基金This work was supported by the National Natural Science Foundation of China (No. 20231020)
文摘The self-assembly of a flexible bipyridyl ligand 2,2?-bis(4-pyridylmethyle- neoxy)-1,1?-biphenylene (4,4?-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4?-bpp)2(SCN)2?H2O]n 1 which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in monoclinic, space group C2/c with unit cell parameters: a = 13.1888(13), b = 24.230(2), c = 15.4218(17) ?, β = 93.291(6)o, V = 4920.1(8) ?3, Z = 4, C50H42CoN6O5S2, Mr = 929.95, Dc = 1.255 g/cm3, F(000) = 1932 and μ(MoKα) = 0.484 mm-1. The final R and wR are 0.0691 and 0.1670 for 3746 observed reflections with I > 2σ(I). 1 possesses an infinite 1-D polymeric chain structure consisting of the repeated basic square units Co2(μ-4,4?-bpp)2, where the Co(II) center acts as the joint of the square ring. The Co(II) center is coordinated in a slightly distorted octahedral geometry with four nitrogen atoms from four different 4,4?-bpp ligands in the equatorial plane and two trans thiocyanate ligands occupying the axial positions, preventing the formation of an extended framework.
