[Cu2(μ-dimethylglyoximato)4] | 29806-01-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [Cu2(μ-dimethylglyoximato)4]
• 英文别名: [Cu2(μ-Hdmg)4]
• CAS: 29806-01-7
• 化学式: C₁₆H₂₈Cu₂N₈O₈
• 分子量: 587.539
• InChiKey: ZTKZYHBYFODZSH-JRDGTKAFSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,2'-联吡啶 、 copper(II) perchlorate hexahydrate 、 [Cu2(μ-dimethylglyoximato)4] 在 triethyl amine 作用下， 以 甲醇 、 水 为溶剂， 以70%的产率得到[Cu4(μ-Hdmg)2(μ-dmg)2(bpy)2(H2O)2](ClO4)2
  参考文献：
  名称：

  Formation of out of plane oxime metallacycles in [Cu2] and [Cu4] complexes

  摘要：

  The reaction Of Cu(ClO4)(2)center dot 6H(2)O with dimethylglyoxime (H(2)dmg) in a 1:1 mole ratio in aqueous methanol at room temperature affords the dinuclear complex [Cu-2(mu-Hdmg)(4)] (1). Reaction of 1 with [Cu(bpy)(H2O)(2)](ClO4)(2) (bpy = 2,2'-bipyridine) in a 1:1 mole ratio in aqueous methanol at room temperature yields the tetranuclear complex [Cu-2(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H2O)(2)](ClO4)(2) (2). The direct reaction of Cu(ClO4)(2)center dot 6H(2)O with H(2)dmg and bpy in a 2:21 mole ratio in aqueous methanol at room temperature also yields 2 quantitatively. The complexes 1 and 2 were structurally characterized by X-ray crystallography. Unlike the binding in Ni/Co-dmg, two different types of N-O bridging modes during the oxime based metallacycle formation and stacking of square planar units have been identified in these complexes. The neutral dinuclear complex 1 has CuN4O coordination spheres and complex 2 consists of a dicationic [Cu-2(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H2O)(2)](2+) unit and two uncoordinated ClO4- anions having CuN4O and CuN2O3 coordination spheres. The two copper(II) ions are at a distance of 3.846(8) angstrom in 1 for the trans out of plane link and at 3.419(10) and 3.684(10) angstrom in 2 for the trans out of plane and cis in plane arrangements, respectively. The average Cu-N-oxime distances are 1.953 and 1.935 angstrom, respectively. The average basal and apical Cu-N-oxime distances are 1.945, 2.295 and 2.429 angstrom. The UV-Vis spectra of 2 is similar to the spectrum of the reaction mixture of 1 and [Cu(bpy)(H2O)(2)](2+). Variable temperature magnetic properties measurement shows that the interaction between the paramagnetic copper centers in complex I is antiferromagnetic in nature. The EPR spectra of frozen solution of the complexes at 77 K consist of axially symmetric fine-structure transitions (Delta M-S = 1) and half-field signals (Delta M-S = 2) at ca. 1600 G, suggesting the presence of appreciable Cu-Cu interactions. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2009.09.019
• 作为产物：
  描述：

  copper(II) perchlorate hexahydrate 、 二甲基乙二醛肟 在 triethyl amine 作用下， 以 甲醇 、 水 为溶剂， 以90%的产率得到[Cu2(μ-dimethylglyoximato)4]
  参考文献：
  名称：

  Formation of out of plane oxime metallacycles in [Cu2] and [Cu4] complexes

  摘要：

  The reaction Of Cu(ClO4)(2)center dot 6H(2)O with dimethylglyoxime (H(2)dmg) in a 1:1 mole ratio in aqueous methanol at room temperature affords the dinuclear complex [Cu-2(mu-Hdmg)(4)] (1). Reaction of 1 with [Cu(bpy)(H2O)(2)](ClO4)(2) (bpy = 2,2'-bipyridine) in a 1:1 mole ratio in aqueous methanol at room temperature yields the tetranuclear complex [Cu-2(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H2O)(2)](ClO4)(2) (2). The direct reaction of Cu(ClO4)(2)center dot 6H(2)O with H(2)dmg and bpy in a 2:21 mole ratio in aqueous methanol at room temperature also yields 2 quantitatively. The complexes 1 and 2 were structurally characterized by X-ray crystallography. Unlike the binding in Ni/Co-dmg, two different types of N-O bridging modes during the oxime based metallacycle formation and stacking of square planar units have been identified in these complexes. The neutral dinuclear complex 1 has CuN4O coordination spheres and complex 2 consists of a dicationic [Cu-2(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H2O)(2)](2+) unit and two uncoordinated ClO4- anions having CuN4O and CuN2O3 coordination spheres. The two copper(II) ions are at a distance of 3.846(8) angstrom in 1 for the trans out of plane link and at 3.419(10) and 3.684(10) angstrom in 2 for the trans out of plane and cis in plane arrangements, respectively. The average Cu-N-oxime distances are 1.953 and 1.935 angstrom, respectively. The average basal and apical Cu-N-oxime distances are 1.945, 2.295 and 2.429 angstrom. The UV-Vis spectra of 2 is similar to the spectrum of the reaction mixture of 1 and [Cu(bpy)(H2O)(2)](2+). Variable temperature magnetic properties measurement shows that the interaction between the paramagnetic copper centers in complex I is antiferromagnetic in nature. The EPR spectra of frozen solution of the complexes at 77 K consist of axially symmetric fine-structure transitions (Delta M-S = 1) and half-field signals (Delta M-S = 2) at ca. 1600 G, suggesting the presence of appreciable Cu-Cu interactions. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2009.09.019