[(1,4,7-triisopropyltriazacyclononane)Cu(CH3CN)]B(C6H5)4 | 184219-38-3

• 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: [(1,4,7-triisopropyltriazacyclononane)Cu(CH3CN)]B(C6H5)4
• 英文别名: Acetonitrile;copper(1+);tetraphenylboranuide;1,4,7-tri(propan-2-yl)-1,4,7-triazonane
• CAS: 184219-38-3
• 化学式: C₁₇H₃₆CuN₄*C₂₄H₂₀B
• 分子量: 679.279
• InChiKey: MROCROLIVWZBKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.72
• 重原子数：
  47
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  33.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2,3,4,5,6,7,8-八硫杂环辛烷 、 [(1,4,7-triisopropyltriazacyclononane)Cu(CH3CN)]B(C6H5)4 以 四氢呋喃 为溶剂， 以37%的产率得到[(1,4,7-triisopropyltriazacyclononane)2Cu2(μ-S2)](BPh4)2
  参考文献：
  名称：

  Reactions of Ph₃Sb═S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity

  摘要：

  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).

  DOI：

  10.1021/ic102449m
• 作为产物：
  描述：

  乙腈 、 copper(l) chloride 、 1,4,7-三氮杂环-N,N',N''-三异丙基壬烷 、 sodium tetrahydroborate 以 四氢呋喃 、 乙腈 为溶剂， 以80%的产率得到[(1,4,7-triisopropyltriazacyclononane)Cu(CH3CN)]B(C6H5)4
  参考文献：
  名称：

  双（μ-氧）二铜配合物的结构、光谱和理论表征，铜介导的双氧活化中的新型中间体

  摘要：

  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

  DOI：

  10.1021/ja962305c

文献信息

• Ligand Macrocycle Structural Effects on Copper−Dioxygen Reactivity
  作者：Bernice M. T. Lam、Jason A. Halfen、Victor G. Young,、John R. Hagadorn、Patrick L. Holland、Agustí Lledós、Lourdes Cucurull-Sánchez、Juan J. Novoa、Santiago Alvarez、William B. Tolman

  DOI：10.1021/ic000248p

  日期：2000.9.1

  supporting ligand influences the relative stability of isomeric mu-eta 2:eta 2-peroxo- and bis(mu-oxo)dicopper complexes, a comparative study was undertaken of the O2 reactivity of Cu(I) compounds supported by the 10- and 12-membered macrocycles, 1,4,7-R3-1,4,7-triazacyclodecane (R3TACD; R = Me, Bn, iPr) and 1,5,9-triisopropyl-1,5,9-triazacyclododecane (iPr3TACDD). While the 3-coordinate complex [(iPr3TACDD)Cu]SbF6

  为了了解三齿大环支撑配体的性质如何影响异构的mu-eTA 2：eTA 2-过氧-和双（mu-oxo）二铜配合物的相对稳定性，进行了对O2反应性的比较研究。由10和12元大环，1,4,7-R3-1、4,7-三氮杂环癸烷（R3TACD; R = Me，Bn，iPr）和1,5,9-三异丙基支撑的Cu（I）化合物-1,5,9-三氮杂环十二烷（iPr3TACDD）。尽管三坐标配合物[（iPr3TACDD）Cu] SbF6与O2不反应，但[-（R3TACD）Cu（CH3CN）] X（R = Me或Bn； X = ClO4-或SbF6-）在-80摄氏度下氧化紫外-可见光谱和共振拉曼光谱表明，生成了双（mu-oxo）物质[（R3TACD）2Cu2（mu O）2] X2。有趣的是，与先前报道的1,4,7-三异丙基-1,4,7-三氮杂环壬烷（iPr3TACN）支持的系统不同，产生过氧化合物和双（mu-oxo）化合物的互变混合物（Cahoy，J