The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2...The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.展开更多
In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip ...In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).展开更多
The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsa...The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.展开更多
An O-Vanillin-methionine Schiff Base complex with copper(Ⅱ) has been synthesized under a mild condition. The complex has been characterized by elemental analysis, UV, FT-IR, TG-DTA and XRD. The crystal structure of t...An O-Vanillin-methionine Schiff Base complex with copper(Ⅱ) has been synthesized under a mild condition. The complex has been characterized by elemental analysis, UV, FT-IR, TG-DTA and XRD. The crystal structure of the complex belongs to monoclinic, with space group C2/C, a=2.070 4(12) nm, b=1.431 9(8) nm, c=2.812 9(11) nm, β=133.15(2)°, V=6.084(5) nm 3, Z=8, D c= 0.998 Mg/m 3, F(000)=1 836, final R=0.121 8. The results revealed it is a tetranuclear copper(Ⅱ) complex.展开更多
基金supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (No. KM201010028008)
文摘The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.
文摘In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).
基金Supported by the key Foundation of the Education Department of Hubei Province (No. D20081503)the foundation of the innovative group of the Education Department of Hubei Province (T200802)
文摘The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.
文摘An O-Vanillin-methionine Schiff Base complex with copper(Ⅱ) has been synthesized under a mild condition. The complex has been characterized by elemental analysis, UV, FT-IR, TG-DTA and XRD. The crystal structure of the complex belongs to monoclinic, with space group C2/C, a=2.070 4(12) nm, b=1.431 9(8) nm, c=2.812 9(11) nm, β=133.15(2)°, V=6.084(5) nm 3, Z=8, D c= 0.998 Mg/m 3, F(000)=1 836, final R=0.121 8. The results revealed it is a tetranuclear copper(Ⅱ) complex.
