[(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]PF6 | 154788-32-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]PF6
• 英文别名: acetonitrile;copper(1+);1,4,7-tri(propan-2-yl)-1,4,7-triazonane;hexafluorophosphate
• CAS: 154788-32-6
• 化学式: C₁₇H₃₆CuN₄*F₆P
• 分子量: 505.01
• InChiKey: URXDYSTUVXFAOR-UHFFFAOYSA-N

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：

  [(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]PF6 以 甲醇 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  还原铜蛋白对亚硝酸盐结合和活化的合成建模。生成一氧化氮的铜 (I)-亚硝酸盐配合物的表征

  摘要：

  为了为铜蛋白介导的亚硝酸盐还原中假定的中间体提供优先权，一系列包含 CuI−NO2- 单元的新型配合物，包括单铜 (I)、双铜 (I,I) 和混合价双铜 (I ,II) 和铜 (I)-锌 (II) 物质被制备、充分表征并进行反应性研究，旨在探测它们产生一氧化氮的能力。[LCu(CH3CN)]PF6 (L = Li-Pr3, 1,4,7-triisopropyl-1,4,7-triazacyclononane, or LBn3, 1,4,7-tribenzyl-1,4,7) 溶液的处理-triazacyclononane) 在 MeOH 中与过量的 NaNO2 产生新型二铜 (I,I) 配合物 [(LCu)2(μ-NO2)]PF6。L = Li-Pr3 的配合物被 PPh3 裂解，得到 [Li-Pr3Cu(PPh3)]PF6 和 Li-Pr3Cu(NO2)，这是亚硝酸铜还原酶底物加合物的结构模型。二铜的氧化(I

  DOI：

  10.1021/ja952691i
• 作为产物：
  描述：

  tetrakis(actonitrile)copper(I) hexafluorophosphate 、 1,4,7-三氮杂环-N,N',N''-三异丙基壬烷 以 四氢呋喃 为溶剂， 以80%的产率得到[(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]PF6
  参考文献：
  名称：

  还原铜蛋白对亚硝酸盐结合和活化的合成建模。生成一氧化氮的铜 (I)-亚硝酸盐配合物的表征

  摘要：

  为了为铜蛋白介导的亚硝酸盐还原中假定的中间体提供优先权，一系列包含 CuI−NO2- 单元的新型配合物，包括单铜 (I)、双铜 (I,I) 和混合价双铜 (I ,II) 和铜 (I)-锌 (II) 物质被制备、充分表征并进行反应性研究，旨在探测它们产生一氧化氮的能力。[LCu(CH3CN)]PF6 (L = Li-Pr3, 1,4,7-triisopropyl-1,4,7-triazacyclononane, or LBn3, 1,4,7-tribenzyl-1,4,7) 溶液的处理-triazacyclononane) 在 MeOH 中与过量的 NaNO2 产生新型二铜 (I,I) 配合物 [(LCu)2(μ-NO2)]PF6。L = Li-Pr3 的配合物被 PPh3 裂解，得到 [Li-Pr3Cu(PPh3)]PF6 和 Li-Pr3Cu(NO2)，这是亚硝酸铜还原酶底物加合物的结构模型。二铜的氧化(I

  DOI：

  10.1021/ja952691i

文献信息

• Structural, Spectroscopic, and Theoretical Characterization of Bis(μ-oxo)dicopper Complexes, Novel Intermediates in Copper-Mediated Dioxygen Activation
  作者：Samiran Mahapatra、Jason A. Halfen、Elizabeth C. Wilkinson、Gaofeng Pan、Xuedong Wang、Victor G. Young、Christopher J. Cramer、Lawrence Que,、William B. Tolman

  DOI：10.1021/ja962305c

  日期：1996.1.1

  of the [Cu2(μ-O)2]2+ core was defined by X-ray crystallography for [(d21-LBn3Cu)2(μ-O)2](SbF6)2 and by EXAFS spectroscopy for the complexes capped by LBn3 and LiPr3; notable dimensions include short Cu−O (∼1.80 A) and Cu···Cu (∼2.80 A) distances like those reported for analogous M2(μ-O)2 (M = Fe or Mn) rhombs. The core geometry is contracted compared to those of the bis(μ-hydroxo)dicopper(II) compounds

  对新型双（μ-氧代）二铜配合物及其双（μ-羟基）二铜分解产物的结构和键合的描述来自结合 X 射线晶体学、光谱学和从头算理论研究。化合物 [(LCu)2(μ-O)2]X2 是由 [LCu(CH3CN)]X 的溶液在 -80 °C 下与 O2 反应生成的（L = 1,4,7-tribenzyl-1， 4,7-三氮杂环壬烷，LBn3；1,4,7-三异丙基-1,4,7-三氮杂环壬烷，LiPr3；或 1-苄基-4,7-二异丙基-1,4,7-三氮杂环壬烷，LiPr2Bn；X = 品种阴离子）。[Cu2(μ-O)2]2+ 核的几何形状由 [(d21-LBn3Cu)2(μ-O)2](SbF6)2 的 X 射线晶体学和封端配合物的 EXAFS 光谱学定义通过 LBn3 和 LiPr3；值得注意的尺寸包括短 Cu-O (∼1.80 A) 和 Cu…Cu (∼2. 80 A) 距离，类似于对类似 M2(μ-O)2
• Halfen, Jason A.; Mahapatra, Samiran; Olmstead, Marilyn M., Journal of the American Chemical Society, 1994, vol. 116, # 5, p. 2173 - 2174
  作者：Halfen, Jason A.、Mahapatra, Samiran、Olmstead, Marilyn M.、Tolman, William B.

  DOI：——

  日期：——
• Experimental Studies of the Interconversion of μ-η²:η²-Peroxo- and Bis(μ-oxo)dicopper Complexes
  作者：John Cahoy、Patrick L. Holland、William B. Tolman

  DOI：10.1021/ic990095+

  日期：1999.5.1

  The effects of solvent composition, counterion, and temperature on the equilibrium between the isomeric complexes [((LCu)-Cu-iPr3)(2)(mu-eta(2):eta(2)-O-2)]X-2 [1(X)(2)] and [((LCu)-Cu-iPr3)(2)(mu-O)(2)]X-2 [2(X)(2); L-iPr3 = 1,4,7-triisopropyl-1,4,7-triazacyclononane; X = PF6-, ClO4-, or SbF6-], which differ with respect to the presence and absence, respectively, of an O-O bond, were examined via solution conductivity and W-vis and resonance Raman spectroscopic measurements. While previous work (Halfen, J. A.; Mahapatra, S.; Wilkinson, E. C.; Kaderli, S.; Young, V. G., Jr.; Que, L., Jr.; Zuberbuhler, A. D.; Tolman, W. B. Science 1996, 271, 1397-1400) had shown that 2(X)(2) (X = PF6- or ClO4-) formed exclusively in THF solution at concentrations >1 mM, new experimental results show that preferential aggregation/precipitation of 2(X)(2) occurs under these conditions. By using lower concentrations and/or X = SbF6-, apparently homogeneous solutions of mixtures of 1(X)(2) and 2(X)(2) in equilibrium in THF and THF/CH2Cl2 mixtures are generated. Evaluation of the temperature dependence of the equilibrium in THF allowed estimation of thermodynamic parameters [Delta H = 0.9(2) kcal mol(-1) and Delta S = 6(1) cal mol(-1) K-1] that are consistent with the small energetic differences between analogous isomers previously calculated using theoretical methods. Tn addition, by avoiding the selective aggregation/precipitation of 2(X)(2), the 1(X)(2)/2(X)(2) equilibrium was shown to exhibit a smooth dependence on the THF:CH2Cl2 ratio in solvent mixtures. The observed gradual shifts in the proportion of the equilibrating isomers as a function of solvent and temperature show that subtle environmental factors influence the equilibrium in similarly subtle ways, with implications for the potential involvement of both types of cores in biological and other catalytic processes.