α-(C-racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate | 51372-01-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: α-(C-racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate
• 英文别名: [(5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) nickel(II)] perchlorate；(5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)nickel(II) perchlorate；Ni(II)(dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)(ClO4)2；[Ni(meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)](ClO₄)₂；[Ni(II)(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)](ClO₄)₂；[Ni(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradecane)](ClO4)2
• CAS: 51372-01-1
• 化学式: C₁₆H₃₆N₄Ni*2ClO₄
• 分子量: 542.08
• InChiKey: UYNGBWJLMQMQSO-DUFSSLHGSA-M

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：
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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：
  None
• 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：

  α-(C-racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate 在 sodium azide 、 ammonium tetrafluoroborate 、 sodium perchlorate 作用下， 以 甲醇 、 水 为溶剂， 生成 肼
  参考文献：
  名称：

  Ngai, Raymond; Wang, Yueh-Hwa L.; Reed, James L., Inorganic Chemistry, 1985, vol. 24, # 23, p. 3802 - 3807

  摘要：

  DOI：
• 作为产物：
  描述：

  (meso-1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate 在 HClO₄ 、 NaOH 作用下， 以 水 、 乙腈 为溶剂， 生成 α-(C-racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate
  参考文献：
  名称：

  Stepwise selective reaction of two N-cyanoethyl groups attached to C-racemic tetraaza macrocyclic nickel(II) and copper(II) complexes in aqueous solutions

  摘要：

  Stepwise hydrolysis of two N-(CH2)(2)CN groups attached to [Ni(C-racemic-L-2)(OAc)](+) and [Cu(C-racemic-L-2)](2+) (L-2 = 1,8-bis(N-cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been investigated. The reaction of [Ni(C-meso-L-2)](2+) has also been examined. Interestingly, [Ni(C-racemic-L-2)(OAc)](+) is readily hydrolyzed to [Ni(C-racemic-L-3)](2+) bearing one N-(CH2)(2)CONH2 and one N-(CH2)(2)CN pendant arms at pH <= 6, whereas [Cu(C-racemic-L-2)](2+) and [Ni(C-meso-L-2)](2+) are quite inert against hydrolysis under similar acidic conditions. Although [Cu(C-racemic-L-2)](2+) is hydrolyzed to [Cu(C-racemic-L-3)](2+) at pH 9, [Ni(C-meso-L-2)](2+) readily undergoes C-N bond cleavage to yield [Ni(C-meso-L-1)](2+) (L-1 = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in basic aqueous solutions. The hetero-functionalized complex [Ni(C-racemic-L-3)](2+) undergoes hydrolysis and C-N bond cleavage at pH 9 and 13, respectively; both [Ni(C-racemic-L-4)](2+) bearing two N-(CH2)(2)CONH2 pendant arms and [Ni(C-racemic-L-5)](2+) bearing one N-(CH2)(2)CONH2 group can be prepared selectively by controlling pH of the solution. However, [Cu(C-racemic-L-3)](2+) readily undergoes C-N bond cleavage to produce [Cu(C-racemic-L-5)](2+) even at pH 9. Crystal structure of [Ni(C-racemic-L-3)](2+) shows that the complex has severely distorted trigonal bipyramidal coordination geometry. Electronic absorption spectra of [Cu(C-racemic-L-3)](2+), [Ni(C-racemic-L-5)](2+), and [Cu(C-racemic-L-5)](2+) indicate that they also have trigonal bipyramidal coordination geometry. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.11.003
• 作为试剂：
  描述：

  3-(2-bromo-1,1-diphenylethoxy)propene 在 高氯酸铵 、 α-(C-racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate 、 高氯酸四乙基铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以44%的产率得到2,2-diphenyl-4-methyltetrahydrofuran
  参考文献：
  名称：

  使用镍（II）配合物作为电子转移催化剂的卤代醚间接电还原自由基环化

  摘要：

  卤代醚的间接电化学自由基环化是在温和的条件下使用镍（II）配合物作为电子转移催化剂实现的。

  DOI：

  10.1039/c39920001120

文献信息

• Structural and Magnetic Diversity in Cyano-Bridged Bi- and Trimetallic Complexes Assembled from Cyanometalates and [M(<i>r</i><i>ac</i>-CTH)]<i>ⁿ</i>⁺ Building Blocks (CTH = <i>d,l</i>-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane)
  作者：Antonio Rodríguez-Diéguez、Raikko Kivekäs、Reijo Sillanpää、Joan Cano、Francesc Lloret、Vickie McKee、Helen Stoeckli-Evans、Enrique Colacio

  DOI：10.1021/ic061187j

  日期：2006.12.1

  coordination positions, and [M(CN)6]3- (M = FeIII, CrIII) and [Fe(CN)2(bpy)2]+ cyanometalate building blocks. The assembled systems, which have been characterized by X-ray crystallography and magnetic investigations, are the molecular squares (meso-CTH-H2)[Ni(rac-CTH)}2Fe(CN)6)}2].5H2O (2) and [Ni(rac-CTH)}2Fe(CN)2(bpy)2}2](ClO4)4.H2O (5), the bimetallic chain [Ni(rac-CTH)}2Cr(CN)6)}2Ni(meso-CTH)].4H2O

  通过组装具有两个顺式可用配位的[M'（rac-CTH）] n +配合物（M'= CrIII，NiII，CuII），制备了七个新的氰基桥杂金属系统。 3-（M = FeIII，CrIII）和[Fe（CN）2（bpy）2] +氰基金属酸盐结构单元。已通过X射线晶体学和磁学研究表征的组装系统是分子正方形（meso-CTH-H2）[Ni（rac-CTH）} 2 Fe（CN）6）} 2] .5 （2）和[Ni（rac-CTH）} 2 Fe（CN）2（bpy）2} 2]（ClO4）4.H2O（5），双金属链[Ni（rac-CTH）} 2 Cr（CN）6）} 2Ni（meso-CTH）.4 （3），三金属链[Ni（rac-CTH）} 2 Fe（CN）6）} 2Cu（cyclam）] 6 （4 ），五核配合物[Cu（rac-CTH} 3 Fe（CN）6} 2] .2 （6）和[Cu（rac-CTH）}
• Constructions of 1D helical chains with left-handed/right-handed helicity: a correlation between the helicity of 1D chains and the chirality of building blocks
  作者：Xiao-Dan Zheng、Long Jiang、Xiao-Long Feng、Tong-Bu Lu

  DOI：10.1039/b904081a

  日期：——

  The reactions of [Ni(α-SS-L)](ClO4)2/[Ni(α-RR-L)](ClO4)2 with dca− gave two enantiomers of [Ni(SS-L)](dca)2 (S-1) and [Ni(RR-L)](dca)2 (R-1) in acetonitrile/water, and two supramolecular stereoisomers of [Ni(SS-L)]2(dca)3(ClO4)·DMF}n (Δ-2) and [Ni(RR-L)]2(dca)3(ClO4)·DMF}n (Λ-2) in acetonitrile/DMF, respectively (L = 5,5,7,12,12, 14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, dca = dicyanamide, N(CN)2−). While the reaction of racemic [Ni(α-rac-L)](ClO4)2 (containing an equal amount of SS and RR enantiomers) with dca− in acetonitrile/water or acetonitrile/DMF produced a trimer of [Ni(rac-L)(dca)]3·(dca)·(ClO4)2·MeCN (3) rather than S-1/R-1 or Δ-2/Λ-2. X-ray single-crystal analysis reveals that S-1/R-1 and Δ-2/Λ-2 crystallize in a chiral space groupP21, while 3 crystallizes in a centrosymmetric space groupC2/c. In S-1/R-1, the [Ni(SS-L)](dca)2/[Ni(RR-L)](dca)2 monomers are linked through intermolecular hydrogen bonds to form a two-dimensional sheet. While the intermolecular hydrogen bonding linking of [Ni(SS-L)]2(dca)3}+/[Ni(RR-L)]2(dca)3}+ leads to the formation of a 1D right-handed helical chain of Δ-2 and 1D left-handed helical chain of Λ-2, respectively, demonstrating there is a correlation between the helicity of 1D chains and the chirality of building blocks. Complex 3 forms a triangular structure of [Ni(rac-L)(dca)]3}3+, in which the macrocyclic ligand L adopts unsymmetrical RR/RR/SS or RR/SS/SS configurations. The homochiral nature of S-1/R-1 and Δ-2/Λ-2 are confirmed by the results of solid circular dichroism (CD) spectra measurements. The magnetic properties of chiral Δ-2/Λ-2 and achiral 3 were investigated.

  在乙腈/水中，[Ni(α-SS-L)](ClO4)2/[Ni(α-RR-L)]( )2 与 dca-反应生成了[Ni(SS-L)](dca)2 (S-1)和[Ni(RR-L)](dca)2 (R-1)两种对映体、以及[Ni(SS-L)]2(dca)3( )-DMF}n (Δ-2)和[Ni(RR-L)]2(dca)3( )-DMF}n (Λ-2)在乙腈/DMF 中的两种超分子立体异构体、L=5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷，dca=双氰胺，N(CN)2-）。外消旋[Ni(α-rac-L)]( )2（含有等量的 SS 和 RR 对映体）与 dca- 在乙腈/水或乙腈/DMF 中反应产生了[Ni(rac-L)(dca)]3-(dca)-( )2-MeCN (3)三聚体，而不是 S-1/R-1 或 Δ-2/Λ-2。X 射线单晶分析表明，S-1/R-1 和 Δ-2/Λ-2 在手性空间群 P21 中结晶，而 3 在中心对称空间群 C2/c 中结晶。在 S-1/R-1 中，[Ni(SS-L)](dca)2/[Ni(RR-L)](dca)2 单体通过分子间氢键连接形成二维薄片。而[Ni(SS-L)]2(dca)3}+/[Ni(RR-L)]2(dca)3}+的分子间氢键连接则分别形成了Δ-2的一维右旋螺旋链和Λ-2的一维左旋螺旋链，这表明一维链的螺旋度与构建模块的手性之间存在相关性。配合物 3 形成了[Ni(rac-L)(dca)]3}3+的三角形结构，其中大环配体 L 采用非对称的 RR/RR/SS 或 RR/SS/SS 构型。固体圆二色性（CD）光谱测量结果证实了 S-1/R-1 和 Δ-2/Λ-2 的同手性。研究了手性 Δ-2/Λ-2 和非手性 3 的磁性。
• Dialkylcarbamato Complexes of Ni(II), Zn(II), and Cd(II)–Tetraazacycloalkanes Obtained from CO₂-Uptake, and X-Ray Structure of (Diethylcarbamato)((7<i>RS</i>,14<i>RS</i>)5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane)nickel(II) Perchlorate
  作者：Haruko Ito、Tasuku Ito

  DOI：10.1246/bcsj.58.1755

  日期：1985.6

  b=13.675(3), c=13.753(2) A, β=109.94(1)°) shows that it is a discrete six-coordinate complex with cis-NiO2N4 geometry, and the carbamato ligand is bidentate. Desired carbamato complexes were hardly obtained with [M(L)]2+ containing tetraaza macrocyclic ligand which favors square-planar coordination. All the data indicate that carbamate ions chelate the metals, and thus use of tetraazacycloalkanes

  某些四氮杂环烷烃 (L) 的镍 (II)、锌 (II) 和镉 (II) 配合物 [M(L)](ClO4)2 吸收 CO2 作为 R2N − 生成氨基甲酸配合物 [M(O2CNR2) (L)]+，其中 L=(7RS,14RS)-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷 (L1) 对于 M=Ni2+，L=1 ,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷 (L2) 对于 M=Ni2+、Zn2+ 和 Cd2+。所得配合物已通过IR、NMR或电子光谱法表征。[Ni(O2CN(C2H5)2)(L1)] 的 X 射线分析（单斜 C2/c，a=15.842(3)，b=13.675(3)，c=13.753(2) A，β=109.94 (1)°) 表明它是一个离散的六配位配合物，具有顺式 NiO2N4 几何结构，并且氨基甲酸配体是双齿的。使用 [M(L)]2+
• Oxidation of tetraaza macrocyclic complexes of nickel(II) with peroxobisulfate ions
  作者：S. V. Rosokha、Ya. D. Lampeka

  DOI：10.1007/bf00534421

  日期：——

  oxidation of some tetraaza macrocyclic complexes of nickel (II) with peroxobisulfate ions in perchloric and sulfuric acid solutions. A scheme of the processes taking place has been proposed and the activation parameters of the reactions determined. The influence of different factors (pH value, ionic strength of the solution, temperature) on the kinetic parameters of the oxidation reactions has been studied

  分光光度法已用于研究镍 (II) 的某些四氮杂大环配合物与过硫酸氢根离子在高氯和硫酸溶液中的氧化动力学。已经提出了发生的过程的方案并确定了反应的活化参数。研究了不同因素（pH 值、溶液的离子强度、温度）对氧化反应动力学参数的影响。已经注意到复合物中大环配体的构象对过程速率的显着影响。
• Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)₆]^3- (M = Mn^III and Fe^III), and [M(N₄-macrocycle)]²⁺ (M = Fe^III, Ni^II and Zn^II) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties
  作者：Enrique Colacio、Mustapha Ghazi、Helen Stoeckli-Evans、Francesc Lloret、José María Moreno、Cristina Pérez

  DOI：10.1021/ic0103446

  日期：2001.9.1

  ion of the [Fe(cyclam)](3+) unit. The isostructural substitution of [Fe(CN)(6)](3-) by [Mn(CN)(6)](3-) in the previously reported complex [Ni(cyclam)](3)[Fe(CN)(6)](2).12H(2)O 2 leads to [Ni(cyclam)](3)[Mn(CN)(6)](2).16 H(2)O 3, which exhibits a corrugated 2D honeycomblike structure and a metamagnetic behavior with T(N) = 16 K and a critical field of 1 T. In the ferromagnetic phase (H > 1 T) this compound

  [M（N（4）-macrocycle）]（2+）之间的反应（M = Zn（II）和Ni（II）；大环配体为CTH = d，l-5,5,7,12,12， 14-六甲基-1,4,8,11-四氮杂环十四烷或cyclam = 1,4,8,11-四氮杂二十四烷）和[M（CN）（6）]（3-）（M = Fe（III）和Mn（ III））产生具有1D线性链和2D蜂窝状结构的氰基桥组装体。对一维线性链复合物[Fe（cyclam）] [Fe（CN）（6）]。6H（2）O 1的磁性测量指出其超磁行为，其中铁磁相互作用在链中起作用，而反铁磁相互作用链。尼尔温度T（N）为5.5 K，2 K时的临界场为1T。基于低自旋Fe（III）离子的轴向拉长的八面体几何形状，可以合理地预料不到铁磁性链内相互作用[Fe（cyclam）]（3+）单位。这一事实可能是由于该化合物中层间距离的增加所致。（[Zn（cyclam）Fe（CN）（6）Zn（cyclam）]