Cu(II)(N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-diiminoquinone) | 252879-21-3

• 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: Cu(II)(N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-diiminoquinone)
• CAS: 252879-21-3
• 化学式: C₃₄H₄₆CuN₂O₂
• 分子量: 578.297
• InChiKey: OGKLBNUUZJNQFR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  copper(II) perchlorate hexahydrate 、 N,N?-双(3,5二叔丁基-2-羟基苯基)-邻苯二胺 在 triethylamine 作用下， 以 甲醇 为溶剂， 以70%的产率得到Cu(II)(N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-diiminoquinone)
  参考文献：
  名称：

  Aerobic Oxidation of Primary Alcohols (Including Methanol) by Copper(II)− and Zinc(II)−Phenoxyl Radical Catalysts

  摘要：

  The tetradentate ligand N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine, H4L(1), has been prepared, and its square planar complexes [Cu-II(L-3)] and [Zn-II(L3)] have been synthesized from the reaction of H4L(1) with [Cu-1(NCCH3)4](ClO4) or Zn(BF4)(2). 2H(2)O in methanol in the presence of air. The dianion (L-3)(2-) represents the two-electron oxidized form of (L-1)(4-), namely N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2- diiminoquinone. Complexes [Cu-II(L-3)]. CH3CN and [Zn(L-3)] CH3CN have been characterized by X-ray crystallography, EPR spectroscopy, and magnetochemistry; [CUII(L-3)] has an S = 1/2 ground state, and [Zn(L-3)] is diamagnetic. Cyclic voltammetry established that both complexes undergo two successive reversible one-electron oxidations and two successive reversible one-electron reductions. Thus, the coordinated ligand exists in five oxidation levels. The species [M-II(L-4)]PF6 (M = Cu-II, Zn-II) and [M-II(L-5)](ClO4)(2) (M = Cu-II, Zn-II) have been isolated and characterized by UV/vis, EPR, and H-1 NMR spectroscopy and by magnetic susceptibility measurements, where (L-4)(-) represents the monoanion N-(3,5-di-tert-butyl-2-hydroxyphenyl) N'-(3,5-di-tert-butyl-2-phenoxyl)-1,2-diiminoquinone and (L5) is the neutral ligand N,N'-bis(3,5-di-tert-butyl-2-phenoxyl)-1,2-diiminoquinone. Similarly, two complexes of the type [M-II((LH2)-H-1)] (M = Cu-II Zn-II) have been isolated from the reaction of (LH4)-H-1 with CUII(ClO4)2 6H(2)O Or Zn(ClO4)2 6H20 under anaerobic conditions in the presence of NEt3. Complexes [Cu-II(L-4)]PF6 and [Zn(L4)1PF(6)]selectively oxidize primary alcohols (including methanol and ethanol) in a stoichiometric fashion under anaerobic conditions, yielding the corresponding aldehydes and [M-II((LH2)-H-2)](+) (M = Cu-II, Zn-II), where (L-2)(3-) is the trianionic form of N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-diiminosemiquinone. Since the latter reduced forms react rapidly with dioxygen with formation of [M-II(L-4)](+) (M = CU, Zn) and 1 equiv of H2O2 these oxidized species are catalysts for the air oxidation of primary alcohols, including ethanol and methanol, with concomitant formation of H2O2 and aldehydes. The kinetics of the stoichiometric reactions and of the catalyses (initial rate method) have been measured. Large kinetic isotope effects show that H-abstraction from the cr-carbon atom of a coordinated alcoholato ligand is the rate-determining step in all cases.

  DOI：

  10.1021/ja991481t

文献信息

• Biomimetic catalytic aerobic oxidation of C–sp(3)–H bonds under mild conditions using galactose oxidase model compound Cu^IIL
  作者：Xiao-Hui Liu、Hai-Yang Yu、Jia-Ying Huang、Ji-Hu Su、Can Xue、Xian-Tai Zhou、Yao-Rong He、Qian He、De-Jing Xu、Chao Xiong、Hong-Bing Ji

  DOI：10.1039/d2sc02606f

  日期：——

  Developing highly efficient catalytic protocols for C–sp(3)–H bond aerobic oxidation under mild conditions is a long-desired goal of chemists. Inspired by nature, a biomimetic approach for the aerobic oxidation of C–sp(3)–H by galactose oxidase model compound CuIIL and NHPI (N-hydroxyphthalimide) was developed. The CuIIL–NHPI system exhibited excellent performance in the oxidation of C–sp(3)–H bonds to ketones

  开发温和条件下C-sp(3)-H键有氧氧化的高效催化方案是化学家长期以来的目标。受大自然的启发，开发了一种通过半乳糖氧化酶模型化合物 Cu II L 和 NHPI（N-羟基邻苯二甲酰亚胺）对 C-sp(3)-H 有氧氧化的仿生方法。Cu II L-NHPI 体系在 C-sp(3)-H 键氧化成酮方面表现出优异的性能，特别是对于轻质烷烃。仿生催化方案具有广泛的底物范围。机理研究表明，Cu II LH 2分子内氧化还原过程中产生的Cu I自由基中间体对于O 2活化至关重要。动力学实验表明NHPI的激活是速率决定步骤。此外，时间分辨 EPR 结果证明了Cu II L-NHPI 系统中 NHPI 的激活。证明了 C-sp(3)-H 键有氧氧化的持久 PINO（邻苯二甲酰亚胺-N-氧基）自由基机制。