(N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)-methyl)amine)Ni(PhCO2)2H2O | 872993-25-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)-methyl)amine)Ni(PhCO2)2H2O
• 英文别名: [(N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)Ni(H2O)(benzoato)2]
• CAS: 872993-25-4
• 化学式: C₄₄H₃₈N₄NiO₅
• 分子量: 761.5
• InChiKey: IYQNAVXVXNCJMN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  高氯酸铵 、 (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)-methyl)amine)Ni(PhCO2)2H2O 以 乙腈 为溶剂， 以70%的产率得到[(6-Ph2TPA)Ni(O2CPh)]ClO4
  参考文献：
  名称：

  Carboxylate Coordination Chemistry of a Mononuclear Ni(II) Center in a Hydrophobic or Hydrogen Bond Donor Secondary Environment:  Relevance to Acireductone Dioxygenase

  摘要：

  A series of Ni(II) carboxylate complexes, supported by a chelate ligand having either secondary hydrophobic phenyl groups (6-Ph(2)TPA, N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) or hydrogen bond donors (bnpapa, N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine), have been prepared and characterized. X-ray crystallographic studies of [(6-Ph(2)TPA)Ni(O2C(CH2)(2)SCH3)]ClO4 center dot CH2Cl2 (4 center dot CH2Cl2) and [(6-Ph(2)TPA)Ni(O2CCH2SCH3)]ClO4 center dot 1.5CH(2)Cl(2) (5 center dot 1.5CH(2)Cl(2)) revealed that each complex contains a distorted octahedral Ni(II) center and a bidentate carboxylate ligand. A previously described benzoate complex ([(6-Ph(2)TPA)Ni(O2CPh)]ClO4 (3)) has similar structural characteristics. Recrystallization of dry powdered samples of 3, 4 center dot 0.5CH(2)Cl(2), and 5 from wet organic solvents yielded a second series of crystalline Ni(II) carboxylate complexes having a coordinated monodentate carboxylate ligand ([(6-Ph(2)TPA)Ni(H2O)(O2CPh)]ClO4 (6), [(6-Ph(2)TPA)Ni(H2O)(O2C(CH2)(2)SCH3)]ClO4 center dot 0.2CH(2)Cl(2) (7 center dot 0.2CH(2)Cl(2)), [(6-Ph(2)TPA)Ni(H2O)(O2CCH2SCH3)]ClO4 (8)) which is stabilized by a hydrogen-bonding interaction with a Ni(II)-bound water molecule. In the cationic portions of 7 center dot 0.2CH(2)Cl(2) and 8, weak CH/pi interactions are also present between the methylene units of the carboxylate ligands and the phenyl appendages of the 6-Ph(2)TPA ligands. A formate complex of the formulation [(6-Ph(2)TPA)Ni(H2O)(O2CH)]ClO4 (9) was isolated and characterized. The mononuclear Ni(II) carboxylate complexes [(bnpapa)Ni(O2CPh)]ClO4 (10), [(bnpapa)Ni(O2C(CH2)(2)SCH3)]ClO4 (11), [(bnpapa)Ni(O2CCH2SCH3)]ClO4 (12), and [(bnpapa)Ni(O2CH)]ClO4 (13) were isolated and characterized. Two crystalline solvate forms of 10(10 center dot CH3CN and 10 center dot CH2Cl2) were examined by X-ray crystallography. In both, the distorted octahedral Ni(II) center is ligated by a bidentate benzoate ligand, one Ni(II)-bound oxygen atom of which accepts two hydrogen bonds from the supporting bnpapa chelate ligand. Spectroscopic studies of 10-13 suggest that all contain a bidentate carboxylate ligand, even after exposure to water. The combined results of this work enable the formulation of a proposed pathway for carboxylate product release from the active site Ni(II) center in acireductone dioxygenase.

  DOI：

  10.1021/ic061316w
• 作为产物：
  描述：

  [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 在 (CH₃)4NOH*6H₂O 、 O₂ 作用下， 以 乙腈 为溶剂， 生成 (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)-methyl)amine)Ni(PhCO2)2H2O
  参考文献：
  名称：

  乙酰苯双加氧酶模型反应中生成的己烯对映体簇

  摘要：

  用[ Me 6 NOH·5H ]处理[（6-Ph 2 TPA）Ni（PhC（O）C（OH）C（O）Ph）] ClO 4（1）会形成烯二醇镍（II）簇（2）2 ○在CH 3 CN。2的晶体学研究显示具有{{Ni（PhC（O）C（O）C（O）Ph）（CH 3 OH）]·1.33CH 3 OH} 6的分子式为S 6的对称六核结构。因为从涉及1的反应中分离出大量2证明是不可能的，所以溶剂化类似物2（标记为5）是由Ni（ClO 4）2 ·6H 2 O，2-羟基-1,3-二苯丙烷-1,3-二酮和Me 4 NOH·5H 2 O在CH 3 OH / CH 3 CN中的混合物生成的。基于元素分析，分子量测定，将络合物5配制成{[Ni（PhC（O）C（O）C（O）Ph）（H 2 O）]·H 2 O·0.25CH 3 CN} 6，紫外可见光和磁矩测量。用O 2和6-Ph 2 TPA（6当量）处理5会导致生成CO和[（6-Ph

  DOI：

  10.1021/ic100775m

文献信息

• Aliphatic Carbon−Carbon Bond Cleavage Reactivity of a Mononuclear Ni(II) <i>cis</i>-β-Keto−Enolate Complex in the Presence of Base and O₂:  A Model Reaction for Acireductone Dioxygenase (ARD)
  作者：Ewa Szajna、Atta M. Arif、Lisa M. Berreau

  DOI：10.1021/ja056346x

  日期：2005.12.1

  mononuclear Ni(II) cis-beta-keto-enolate complex, [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (1) (6-Ph2TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) are reported. Complex 1 was characterized by X-ray crystallography, elemental analysis, 1H NMR, and electronic absorption and infrared spectroscopy. Treatment of 1 with 1 equiv of Me4NOH.5H2O in the presence of O2 results in oxidative carbon-carbon

  单核 Ni(II) 顺式-β-酮-烯醇化物复合物 [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 的合成、表征和反应特性 (1 ) (6-Ph2TPA = N,N-双((6-苯基-2-吡啶基)甲基)-N-((2-吡啶基)甲基)胺)被报道。配合物 1 的特点是 X 射线晶体学、元素分析、1H 核磁共振、电子吸收和红外光谱。在 O2 存在下用 1 当量 Me4NOH.5 处理 1 导致碳-碳键氧化断裂并形成新的 Ni(II) 二羧酸络合物 [(6-Ph2TPA)Ni(O2CPh)2(H2O) ] (2). 配合物 2 已通过 X 射线晶体学、1H NMR、UV-vis、IR 和元素分析进行​​表征。在 1 生成 2 的反应中使用 18O2 导致大多数样品中每个羧酸盐配体掺入一个 18O 原子。使用氯化钯方法检测在 1 到 2 的氧化转化中产生的 CO。这是第一个与乙酰还原酮双加氧酶