[Zn(O2C(t-Bu))2(4-(dimethylamino)pyridine)2]·H2O | 1431854-12-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [Zn(O2C(t-Bu))2(4-(dimethylamino)pyridine)2]·H2O
• CAS: 1431854-12-4
• 化学式: C₂₄H₃₈N₄O₄Zn*H₂O
• 分子量: 529.995
• InChiKey: QRKDDGSSTLKGLB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
  None
• 环数：
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• 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：

  氯仿 、 [Zn(O2C(t-Bu))2(4-(dimethylamino)pyridine)2]·H2O 以 正己烷 、 氯仿 为溶剂， 反应 96.0h， 以77%的产率得到[Zn(O2C(t-Bu))2(4-(dimethylamino)pyridine)2]·CHCl3
  参考文献：
  名称：

  Mole ratio dependent formation of mononuclear versus pentanuclear zinc(II) pivalate complexes and the ‘carboxylate shift’ process

  摘要：

  The reaction of Zn((O2CBu)-Bu-t)(2) with 4-(dimethylamino)pyridine (DMAP) in 1:2 and 1:1 mol ratios afforded [Zn((O2CBu)-Bu-t)(2)(DMAP)(2)]center dot H2O (1 center dot H2O) and [Zn-5(mu(3)-OH)(2)((O2CBu)-Bu-t)(2)(mu(2)-kappa O-1':kappa O-1'-(O2CBu)-Bu-t)(6)(DMAP)(2)] (2) in 95% and 98% yields, respectively. Complex 1 center dot H2O upon crystallization from CHCl3/n-hexane mixture at ambient temperature afforded 1 center dot CHCl3 in 77% yield. Complex 2 upon re-crystallization in a CH2Cl2/n-hexane mixture or CDCl3 at ambient condition afforded a unique pentanuclear complex, [Zn-5(mu(3)-OH)(2)((O2CBu)-Bu-t)(kappa O-2,O'-(O2CBu)-Bu-t)(mu(2)-kappa O-1:kappa O-1'-(O2CBu)-Bu-t)(6)(DMAP)(2)] (3) in 98% yield. Complex 3 upon re-crystallization in methanol transformed back to 2. The new complexes were characterized by elemental analysis, TGA/DTA/DSC analysis, FT-IR, NMR (solution H-1 and C-13, and solid state CP-MAS) spectroscopy, and selected complexes were characterized by single crystal X-ray diffraction. The molecular structures of 2 and 3 represent a crystallographic snapshot of a monodentate <-> chelating 'carboxylate shift' process. Variable temperature H-1 NMR measurements carried out on 2 in methanol-d indicated the presence of two species, possibly 2 and 3, in about a 2:1 ratio, respectively at 198 K suggesting the aforementioned 'carboxylate shift' process operating in solution. Various factors that are responsible for the 'carboxylate shift' process are discussed. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.02.081
• 作为产物：
  描述：

  4-二甲氨基吡啶 、 zinc pivalate 、 水 以 甲醇 为溶剂， 反应 12.0h， 以95%的产率得到[Zn(O2C(t-Bu))2(4-(dimethylamino)pyridine)2]·H2O
  参考文献：
  名称：

  Mole ratio dependent formation of mononuclear versus pentanuclear zinc(II) pivalate complexes and the ‘carboxylate shift’ process

  摘要：

  The reaction of Zn((O2CBu)-Bu-t)(2) with 4-(dimethylamino)pyridine (DMAP) in 1:2 and 1:1 mol ratios afforded [Zn((O2CBu)-Bu-t)(2)(DMAP)(2)]center dot H2O (1 center dot H2O) and [Zn-5(mu(3)-OH)(2)((O2CBu)-Bu-t)(2)(mu(2)-kappa O-1':kappa O-1'-(O2CBu)-Bu-t)(6)(DMAP)(2)] (2) in 95% and 98% yields, respectively. Complex 1 center dot H2O upon crystallization from CHCl3/n-hexane mixture at ambient temperature afforded 1 center dot CHCl3 in 77% yield. Complex 2 upon re-crystallization in a CH2Cl2/n-hexane mixture or CDCl3 at ambient condition afforded a unique pentanuclear complex, [Zn-5(mu(3)-OH)(2)((O2CBu)-Bu-t)(kappa O-2,O'-(O2CBu)-Bu-t)(mu(2)-kappa O-1:kappa O-1'-(O2CBu)-Bu-t)(6)(DMAP)(2)] (3) in 98% yield. Complex 3 upon re-crystallization in methanol transformed back to 2. The new complexes were characterized by elemental analysis, TGA/DTA/DSC analysis, FT-IR, NMR (solution H-1 and C-13, and solid state CP-MAS) spectroscopy, and selected complexes were characterized by single crystal X-ray diffraction. The molecular structures of 2 and 3 represent a crystallographic snapshot of a monodentate <-> chelating 'carboxylate shift' process. Variable temperature H-1 NMR measurements carried out on 2 in methanol-d indicated the presence of two species, possibly 2 and 3, in about a 2:1 ratio, respectively at 198 K suggesting the aforementioned 'carboxylate shift' process operating in solution. Various factors that are responsible for the 'carboxylate shift' process are discussed. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.02.081