(N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide)Cu(III)OH | 1339804-26-0

• 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)-2,6-pyridinedicarboxamide)Cu(III)OH
• 英文别名: [Cu(III)(N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide)(OH)]
• CAS: 1339804-26-0
• 化学式: C₃₁H₃₈CuN₃O₃
• 分子量: 564.207
• InChiKey: BSXUFHHBXSIZME-UHFFFAOYSA-K

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：

  (N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide)Cu(III)OH 在 dihydroanthracene 作用下， 以 丙酮 为溶剂， 生成 [Cu(II)(N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide)(OH2)]
  参考文献：
  名称：

  Rapid C–H Bond Activation by a Monocopper(III)–Hydroxide Complex

  摘要：

  One-electron oxidation of the tetragonal Cu(II) complex [Bu4N][LCuOH] at -80 degrees C generated the reactive intermediate LCuOH, which was shown to be a Cu(III) complex on the basis of spectroscopy and theory (L = N,N'-bis(2;6-diisopropylphenyl)-2,6-pyridinedicarboxamide). The complex LCuOH reacts with dihydroanthracene to yield, anthracene and the Cu(II) complex LCu-(OH2). Kinetic studies showed that the reaction occurs via H-atom abstraction via a second order rate law at high rates (cf. k = 1.1(1) M-1 s(-1) at -80 degrees C, Delta H-double dagger = 5.4(2). kcal mol(-1), Delta S-double dagger = -30(2) eu) and with very large kinetic isotope effects.(cf. k(H)/k(D) = 44 at -770 degrees C). The findings suggest that a Cu(III)-OH moiety is a viable reactant in oxidation catalysis.

  DOI：

  10.1021/ja207882h
• 作为产物：
  描述：

  [CuII(NCCH3)(N,N'-bis(2,6-diisoproylphenyl)-2,6-pyridinedicarboxamide)] 在 (C₅H₅)Fe(C₅H₅)PF₆ 作用下， 以 甲醇 、 丙酮 为溶剂， 生成 (N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide)Cu(III)OH
  参考文献：
  名称：

  Rapid C–H Bond Activation by a Monocopper(III)–Hydroxide Complex

  摘要：

  One-electron oxidation of the tetragonal Cu(II) complex [Bu4N][LCuOH] at -80 degrees C generated the reactive intermediate LCuOH, which was shown to be a Cu(III) complex on the basis of spectroscopy and theory (L = N,N'-bis(2;6-diisopropylphenyl)-2,6-pyridinedicarboxamide). The complex LCuOH reacts with dihydroanthracene to yield, anthracene and the Cu(II) complex LCu-(OH2). Kinetic studies showed that the reaction occurs via H-atom abstraction via a second order rate law at high rates (cf. k = 1.1(1) M-1 s(-1) at -80 degrees C, Delta H-double dagger = 5.4(2). kcal mol(-1), Delta S-double dagger = -30(2) eu) and with very large kinetic isotope effects.(cf. k(H)/k(D) = 44 at -770 degrees C). The findings suggest that a Cu(III)-OH moiety is a viable reactant in oxidation catalysis.

  DOI：

  10.1021/ja207882h

文献信息

• Structural Characterization of the [CuOR]²⁺ Core
  作者：V. Mahesh Krishnan、Dimitar Y. Shopov、Caitlin J. Bouchey、Wilson D. Bailey、Riffat Parveen、Bess Vlaisavljevich、William B. Tolman

  DOI：10.1021/jacs.0c13470

  日期：2021.3.10

  Formal Cu(III) complexes bearing an oxygen-based auxiliary ligand ([CuOR]2+, R = H or CH2CF3) were stabilized by modulating the donor character of supporting ligand LY (LY = 4-Y, N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide, Y = H or OMe) and/or the basicity of the auxiliary ligand, enabling the first characterization of these typically highly reactive cores by NMR spectroscopy and X-ray

  通过调节支持配体 L Y ( L Y = 4 - Y , N , N '-双(2,6-二异丙基苯基)-2,6-吡啶二甲酰胺, Y = H 或 OMe) 和/或辅助配体的碱度, 能够通过 NMR 光谱和 X 首次表征这些典型的高反应性核- 射线晶体学。观察到苯酚底物在溶液中的寿命延长和 PCET 速率降低。核磁共振光谱证实了S= 0 配合物的基态，X 射线结构显示缩短的 Cu-配体键距离与理论非常吻合。
• Perturbing the Copper(III)–Hydroxide Unit through Ligand Structural Variation
  作者：Debanjan Dhar、Gereon M. Yee、Andrew D. Spaeth、David W. Boyce、Hongtu Zhang、Büsra Dereli、Christopher J. Cramer、William B. Tolman

  DOI：10.1021/jacs.5b10985

  日期：2016.1.13

  were further probed by evaluating the rates of HAT by the corresponding Cu(III)-hydroxide complexes from substrates with C-H bonds of variable strength. These studies revealed an overarching linear trend in the relationship between the log k (where k is the second-order rate constant) and the ΔH of reaction. Additional subtleties in measured rates arise, however, that are associated with variations in

  两个新配体组，(pipMe)LH2 和 (NO2)LH2 ((pipMe)L = N,N'-双(2,6-二异丙基苯基)-1-甲基哌啶-2,6-二甲酰胺，( )L = N据报道，N'-双（2,6-二异丙基-4-硝基苯基）吡啶-2,6-二甲酰胺）旨在扰乱氢氧化铜（III）核的整体电子学以及由此产生的影响其氢原子夺取（HAT）反应的热力学和动力学。测量了相应 Cu(II)-OH2 配合物的 OH 键的键解离能 (BDE)，结果表明 Cu(III)/Cu(II) 对氧化还原电位的变化仅部分被pKa，导致三种化合物之间的 BDE 存在一定差异。通过评估来自具有不同强度的 CH 键的底物的相应 Cu(III)-氢氧化物复合物的 HAT 速率，进一步探讨了这些变化的影响。这些研究揭示了 log k（其中 k 是二阶速率常数）和反应 ΔH 之间关系的总体线性趋势。然而，测量速率中出现了其他微妙之处，这些变化与
• Reactivity of (Dicarboxamide)M ^II –OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield M ^II –Cyanomethides
  作者：Jacqui Tehranchi、Patrick J. Donoghue、Christopher J. Cramer、William B. Tolman

  DOI：10.1002/ejic.201300328

  日期：2013.8.6

  nitrile carbon and formation of amides or carboxylic acids. Kinetic studies (M = Cu) revealed a first-order dependence on the complex and a kinetic isotope effect (k(CH3CN)/k(CD3CN) of 4. Various mechanisms involving either intra- or intermolecular deprotonation steps are proposed. In addition, (Bu4N)(LMeCu-OH) was oxidized by Fc+PF6- to a proposed Cu(III) complex LMeCuOH at low temperature, and comparisons

  配合物 (Bu4N)(LMeM(II)-OH)（LMe = 2,6-二甲基苯基取代的吡啶（二甲酰胺）；M = Cu 或 Ni）与 CH3CN 反应生成 (Bu4N)(LMeM-CH2CN)，新型氰基甲基化物完全表征的复合物，包括 X 射线晶体学。这些转化与金属氢氧化物配合物与腈的通常反应形成对比，后者通常涉及对腈碳的攻击和酰胺或羧酸的形成。动力学研究 (M = Cu) 揭示了对复合物的一级依赖性和动力学同位素效应 (k(CH3CN)/k(CD3CN) 为 4。提出了涉及分子内或分子间去质子化步骤的各种机制。此外， (Bu4N)(LMeCu-OH) 在低温下被 Fc+PF6- 氧化为建议的 Cu(III) 络合物 LMeCuOH，并将其稳定性和与二氢蒽的反应性与其先前描述的在支持配体的苯环上具有异丙基取代基的同类物进行比较。氰基甲基化物络合物 (Bu4N)(LMeCu(CH2CN)) 也被电化学（E1/2