| 251326-24-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 251326-24-6
• 化学式: C₂H₃N*C₃₄H₄₄CuN₂O₂
• 分子量: 617.334
• InChiKey: FTLFFFQEXKADAI-DWMVAVLBSA-L

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

• 作为产物：
  描述：

  tetrakis(acetonitrile)copper(I) perchlorate 、 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49%的产率得到
  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