[(6-Ph2TPA)Ni(O2CPh)]ClO4 | 932703-85-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(6-Ph2TPA)Ni(O2CPh)]ClO4
• 英文别名: [(N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)Ni(benzoato)]ClO4；[(6-Ph2TPA)Ni(PhCO2)](ClO4)；nickel(2+);1-(6-phenylpyridin-2-yl)-N-[(6-phenylpyridin-2-yl)methyl]-N-(pyridin-2-ylmethyl)methanamine;benzoate;perchlorate
• CAS: 932703-85-0
• 化学式: C₃₇H₃₁N₄NiO₂*ClO₄
• 分子量: 721.819
• InChiKey: QGQVKDVBHXMQCG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  49
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  156
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 在 Me₄NOH*5H₂O 作用下， 以 乙腈 为溶剂， 生成 [(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

文献信息

• Mechanistic Studies of the O₂-Dependent Aliphatic Carbon−Carbon Bond Cleavage Reaction of a Nickel Enolate Complex
  作者：Lisa M. Berreau、Tomasz Borowski、Katarzyna Grubel、Caleb J. Allpress、Jeffrey P. Wikstrom、Meaghan E. Germain、Elena V. Rybak-Akimova、David L. Tierney

  DOI：10.1021/ic1017888

  日期：2011.2.7

  Overall, I is a reasonable structural model for the ES adduct formed in the active site of NiIIARD. However, the presence of phenyl appendages at both C(1) and C(3) in the [PhC(O)C(OH)C(O)Ph]− anion results in a reaction pathway for O2-dependent aliphatic carbon−carbon bond cleavage (via a trione intermediate) that differs from that accessible to C(1)−H acireductone species. This study, as the first detailed

  单核镍（II）烯醇盐配合物[（6-Ph 2 TPA）Ni（PhC（O）C（OH）C（O）Ph] ClO 4（I）是酶/底物（ES的第一个反应模型配合物）待报道的含镍（II）的乙二醛酮双加氧酶（ARDs）中的加合物，进一步研究了其依赖于O 2的脂肪族碳-碳键裂解反应的机理，停止流动力学研究表明该反应的我被O 2是整体二阶和更慢〜80倍，在比涉及烯醇化物盐[Me中反应25℃ 4 N] [光子晶体（O）C（OH）C（O）PH]。计算研究阴离子[PhC（O）C（OH）C（O）Ph] -与O的反应2支持氢过氧化物机构，其中所述第一步骤是氧化还原过程的结果在1,3- diphenylpropanetrione和HOO的形成- 。独立的实验表明，1,3- diphenylpropanetrione和HOO之间的反应-导致氧化脂族碳-碳键裂解和苯甲酸，苯甲酸的形成，和CO：CO 2（〜12：1）。在存在镍
• O₂-Dependent Aliphatic Carbon−Carbon Bond Cleavage Reactivity in a Ni(II) Enolate Complex Having a Hydrogen Bond Donor Microenvironment; Comparison with a Hydrophobic Analogue
  作者：Katarzyna Grubel、Amy L. Fuller、Bonnie M. Chambers、Atta M. Arif、Lisa M. Berreau

  DOI：10.1021/ic901981y

  日期：2010.2.1

  A mononuclear Ni(II) complex having an acireductone type ligand, and supported by the bnpapa (N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) ligand, [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (14), has been prepared and characterized by elemental analysis, 1H NMR, FTIR, and UV−vis. To gain insight into the 1H NMR features of 14, the air stable analogue complexes [(bnpapa)Ni(CH3C(O)CHC(O)CH3)]ClO4

  一种单核 Ni(II) 配合物，具有 acireductone 型配体，并由 bnpapa ( N , N -bis( (6- nepentylamino -2-pyridyl)methyl) -N -((2-pyridyl)methyl)amine) 配体支持, [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO 4 ( 14 ) 已制备并通过元素分析、1 H NMR、FTIR 和 UV-vis 进行表征。为了深入了解14的1 H NMR 特征，空气稳定的类似物复合物 [(bnpapa)Ni(CH 3 C(O)CHC(O)CH 3 )]ClO 4 ( 16 ) 和 [(bnpapa)Ni(ONHC (O)CH 3 )]ClO 4 ( 17) 制备并通过 X 射线晶体学、1 H NMR、FTIR、UV-vis、质谱和溶液电导率测量表征。化合物16和17是 CH 3 CN中
• Acireductone Dioxygenase- (ARD-) Type Reactivity of a Nickel(II) Complex Having Monoanionic Coordination of a Model Substrate:  Product Identification and Comparisons to Unreactive Analogues
  作者：Ewa Szajna-Fuller、Katarzyna Rudzka、Atta M. Arif、Lisa M. Berreau

  DOI：10.1021/ic061177i

  日期：2007.7.1

  N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) and containing a cis-beta-keto-enolate ligand having a C2 hydroxyl substituent, undergoes reaction with O2 to produce a Ni(II) monobenzoate complex ([(6-Ph2TPA)Ni(O2CPh)]ClO4 (3)), CO, benzil (PhC(O)C(O)Ph), benzoic acid, and other minor unidentified phenyl-containing products. Complex 3 has been identified through independent synthesis and was characterized

  单核Ni（II）配合物（[（6-Ph2TPA）Ni（PhC（OCC（OH）C（O）Ph）] ClO4（1）），由6-Ph2TPA螯合配体（6-Ph2TPA = N，N-双（（6-苯基-2-吡啶基）甲基）-N-（（2-吡啶基）甲基）胺并含有具有C2羟基取代基的顺式-β-酮-烯酸酯配体，与O2生成单苯甲酸镍Ni（II）络合物（[（6-Ph2TPA）Ni（O2CPh）] （3）），CO，苯甲腈（PhC（O）C（O）Ph），苯甲酸和其他少量未鉴定的含苯基的产品。配合物3已通过独立合成鉴定，并通过X射线晶体学，1 H NMR，FAB-MS，FTIR和元素分析进行​​了表征。由6-Ph2TPA配体（[（6-Ph2TPA）Ni（PhC（O）CHC（O）Ph）] （4），[（6 -Ph2TPA）Ni（ C（O）CHC（O）CH3）] （5），已经制备并表征了[（6-Ph2TPA