(N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(O2) | 410527-33-2

• 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: (N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(O2)
• 英文别名: (N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(O₂)；[Cu(O2)(N,N'-bis(2,6-diisopropylphenyl)-3,5-pentanediiminato)]；(HC(C(Me)NC6H3-i-Pr2-2,6)2)Cu(III)(η2-peroxo)
• CAS: 410527-33-2
• 化学式: C₂₉H₄₁CuN₂O₂
• 分子量: 513.203
• InChiKey: FJMSCVCQALQDKT-GGFZQTNZSA-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：

  (η2-peroxo)bis(triphenylphosphine)palladium 、 (N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(O2) 以 四氢呋喃 为溶剂， 生成 [(CH(C(CH3)NC6H3(CH(CH3)2)2)2bis(μ-oxo)copper(III)Pd(II)(P(C6H5)3)2]
  参考文献：
  名称：

  Mixed metal bis(μ-oxo) complexes with [CuM(μ-O)₂]ⁿ⁺(M = Ni(iii) or Pd(ii)) cores

  摘要：

  通过将单核过氧物种与还原型金属前体在±80 °C下结合，制备出了两种高活性异核双（δ-氧）配合物，并通过紫外-可见光、EPR/NMR和共振拉曼光谱对其进行了鉴定，同时通过密度泛函计算对铜钯体系进行了确证。

  DOI：

  10.1039/b404640d
• 作为产物：
  描述：

  (N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(acetonitrile) 以 四氢呋喃 为溶剂， 生成 (N,N'-bis-2,6-diisopropylphenyl-2,4-dimethyl-1,5-diketamide)Cu(O2)
  参考文献：
  名称：

  Dioxygen Activation at a Single Copper Site:  Structure, Bonding, and Mechanism of Formation of 1:1 Cu−O₂ Adducts

  摘要：

  To evaluate the fundamental process Of O-2 activation at a single copper site that occurs in biological and catalytic systems, a detailed study Of O-2 binding to Cu(l) complexes of beta-diketiminate ligands L (L-1 = backbone Me; L-2 = backbone tBu) by X-ray crystallography, X-ray absorption spectroscopy (XAS), cryogenic stopped-flow kinetics, and theoretical calculations was performed. Using synchrotron radiation, an X-ray diffraction data set for (LCuO2)-Cu-2 was acquired, which led to structural parameters in close agreement to theoretical predictions. Significant Cu(Ill)-peroxo character for the complex was corroborated by XAS. On the basis of stopped-flow kinetics data and theoretical calculations for the oxygenation of (LCu)-Cu-1(RCN) (R = alkyl, aryl) in THF and THF/RCN mixtures between 193 and 233 K, a dual pathway mechanism is proposed involving (a) rate-determining solvolysis of RCN by THF followed by rapid oxygenation of (LCu)-Cu-1(THF) and (b) direct, bimolecular oxygenation of (LCu)-Cu-1(RCN) via an associative process.

  DOI：

  10.1021/ja045678j

文献信息

• β-Diketiminate Ligand Backbone Structural Effects on Cu(I)/O₂ Reactivity:  Unique Copper−Superoxo and Bis(μ-oxo) Complexes
  作者：Douglas J. E. Spencer、Nermeen W. Aboelella、Anne M. Reynolds、Patrick L. Holland、William B. Tolman

  DOI：10.1021/ja017820b

  日期：2002.3.1

  features of the Cu(I) and Cu(II) complexes and (b) the course of the oxygenation reactions of the Cu(I) compounds. With the less hindered ligand, a rare example of a neutral bis(μ-oxo)dicopper complex was identified on the basis of its diagnostic spectral features (UV−vis, resonance Raman, EPR) and the stoichiometry of O2 uptake (Cu:O2 = 2:1). In contrast, oxygenation of the Cu(I) complexes supported

  制备了具有相同侧翼 2,6-二异丙基苯基但骨架取代模式不同的 β-二酮亚胺配体的铜 (I) 和 -(II) 配合物，并对其进行了结构表征，并且在低温下 Cu(I) 物种与 O2 的反应为探索。尽管远离配位金属离子，但不同的骨架模式显着影响了配体施加的空间阻碍，正如（a）Cu（I）和Cu（II）配合物的结构特征和（b）中的差异所揭示的) Cu(I) 化合物的氧化反应过程。使用受阻较少的配体，根据其诊断光谱特征（UV-vis、共振拉曼、EPR）和 O2 吸收的化学计量（Cu:O2 = 2:1)。相比之下，
• Reactivity of a 1∶1 copper–oxygen complex: isolation of a Cu(<scp>ii</scp>)-o-iminosemiquinonato species
  作者：Anne M. Reynolds、Elizabeth A. Lewis、Nermeen W. Aboelella、William B. Tolman

  DOI：10.1039/b418939f

  日期：——

  While a 1∶1 Cu–O2 adduct is generally unreactive with organic substrates, phosphines displace O2via an associative process and added Cu(I) leads to a novel internal ligand oxidation to yield a Cu(II)-o-iminosemiquinone complex.

  虽然 1â¶1 CuâO2 加合物通常与有机底物没有反应，但膦会通过一个结合过程置换出 O2，而添加的 Cu(I) 则会导致新的内部配体氧化，生成 Cu(II)-o- 亚氨基喹啉酮复合物。
• Snapshots of Dioxygen Activation by Copper:  The Structure of a 1:1 Cu/O₂ Adduct and Its Use in Syntheses of Asymmetric Bis(μ-oxo) Complexes
  作者：Nermeen W. Aboelella、Elizabeth A. Lewis、Anne M. Reynolds、William W. Brennessel、Christopher J. Cramer、William B. Tolman

  DOI：10.1021/ja027164v

  日期：2002.9.1

  The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the

  1:1 Cu/O(2) 加合物的 X 射线结构显示侧面 (eta(2)) O(2) 协调。密度泛函计算证实了结构，表明 Cu(III)-(O(2)(2-)) 共振形式的重要贡献，并提供了对关键键合相互作用的见解。由略微不同的 β-二酮亚胺配体支持的 1:1 加合物与 Cu(I) 试剂的反应导致形成新型不对称双 (mu-oxo) 配合物，该配合物通过 EPR、UV-vis 和拉曼光谱进行鉴定以及在一种情况下通过 X 射线结构。