[(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]SbF6 | 184219-36-1

• 英文名称: [(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]SbF6
• 英文别名: [(1,4,7-triisopropyltriazacyclononane)Cu(CH3CN)]SbF6；[(iPr3tacn)Cu(MeCN)]SbF6
• CAS: 184219-36-1
• 化学式: C₁₇H₃₆CuN₄*F₆Sb
• 分子量: 595.786
• InChiKey: UXCWGTOOMYNYKE-UHFFFAOYSA-H

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：

  (η2-peroxo)bis(triphenylphosphine)palladium 、 [(1,4,7-triisopropyl-1,4,7-triazacyclononane)Cu(CH3CN)]SbF6 以 二氯甲烷 为溶剂， 生成 [(iPr3tacn)Cu(μ-O)2Pd(PPh3)2]SbF6
  参考文献：
  名称：

  异双金属双氧活化：混合 Cu−Pd 和 Cu−Pt Bis(μ-oxo) 配合物的合成和反应性

  摘要：

  通过 (PPh3)2MO2 (M=Pd, Pt) 与 LCu(I) 前体（L=β-二酮亚胺以及二胺和三胺配体）反应制备了异双金属 CuPd 和 CuPt 双（mu-oxo）配合物，并对其进行了表征通过低温 UV-vis、共振拉曼、1H 和 31P[1H] NMR 光谱结合 DFT 计算。这些复合物在升温时分解产生 OPPh3，在一种情况下，通过使用双标记（氧代和膦）的交叉实验表明这是通过分子内过程发生的。其中一种配合物 LMe2Cu(mu-O)2Pt(PPh3)2 (LMe2 = β-二酮亚胺) 与多种试剂（包括 CO2、2,4-二叔丁基苯酚、2,4-二甲基苯酚）的反应性将叔丁基苯酚盐、[NH4][PF6] 和二氢蒽与同质金属 Pt2 和 Cu2 对应物进行比较。与具有亲电子氧基团的典型 [Cu2(mu-O)2]2+ 核心不同，[Cu(mu-O)2Pt]+ 核心中的氧基团充当碱基和亲核试剂，类似于之前描述的

  DOI：

  10.1021/ja071744g

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
• 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.
• Reactions of Ph₃Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity
  作者：Lei Yang、Jacqui Tehranchi、William B. Tolman

  DOI：10.1021/ic102449m

  日期：2011.3.21

  In the exploration of sulfur-delivery reagents useful for synthesizing models of the tetracopper-sulfide cluster of nitrous oxide reductase, reactions of Ph3Sb=S with Cu(I) complexes of N,N,N',N'-tetramethyl-2R,3R-cyclohexanediamine (TMCHD) and 1,4,7-trialkyltriazacyclononanes (R(3)tacn; R = Me, Et, iPr) were studied. Treatment of [(R(3)tacn)Cu(NCCH3)]SbF6 (R = Me, Et, or iPr) with 1 equiv of S=SbPh3 in CH2Cl2 yielded adducts [(R(3)tacn)Cu(S=SbPh3)]SbF6 (1-3), which were fully characterized, including by X-ray crystallography. The adducts slowly decayed to [(R(3)tacn)(2)Cu-2(mu-eta(2):eta(2)-S-2)](2+) species (4-6) and SbPh3, or more quickly in the presence of additional [(R(3)tacn)Cu(NCCH3)]SbF6 to 4-6 and [(R(3)tacn)Cu(SbPh3)]SbF6 (7-9). The results of mechanistic studies of the latter process were consistent with rapid intermolecular exchange of S=SbPh3 between 1-3 and added [(R(3)tacn)Cu(NCCH3)]SbF6, followed by conversion to product via a dicopper intermediate formed in a rapid pre-equilibrium step. Key evidence supporting this step came from the observation of saturation behavior in a plot of the initial rate of loss of 1 versus the initial concentration of [(Me(3)tacn)Cu(NCCH3)]SbF6. Also, treatment of [(TMCHD)Cu(CH3CN)]PF6 with S=SbPh3 led to the known tricopper cluster [(TMCHD)(3)Cu-3(mu(3)-S)(2)](PF6)(3) in good yield (79%), a synthetic procedure superior to that previously reported (Brown, E. C.; York, J. T.; Antholine, W. E.; Ruiz, E.; Alvarez, S.; Tolman, W. B. J. Am. Chem. Soc. 2005, 127, 13752-13753).