(N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IICl₂ | 383883-20-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IICl₂
• 英文别名: [(N,N'-ditertiobutyl-2,11-diaza[3.3](2,6)pyridinophane)PdCl2]；3,11-ditert-butyl-3,11,17,18-tetrazatricyclo[11.3.1.15,9]octadeca-1(17),5(18),6,8,13,15-hexaene;palladium(2+);dichloride
• CAS: 383883-20-3；383883-26-9
• 化学式: C₂₂H₃₂Cl₂N₄Pd
• 分子量: 529.849
• InChiKey: ZSFIZBIPESOGSA-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IICl₂ 、 四丁基高氯酸铵 、 乙腈 以 二氯甲烷 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  The Conformational Flexibility of the Tetradentate Ligand^tBuN4 is Essential for the Stabilization of (^tBuN4)Pd^IIIComplexes

  摘要：

  The conformationally flexible tetradentate pyridinophane ligand (tBu)N4 effectively lowers the oxidation potential of ((tBu)N4)PdII complexes and promotes their facile chemical and electrochemical oxidation, including unpredecented aerobic oxidation reactivity. While the low potential of a number of PdII (and PtII) complexes supported by various fac-chelating polydentate ligands is often attributed to the presence of a coordinating group in the axial position of the metal center, no detailed electrochemical studies have been reported for such systems. Described herein is the detailed electrochemical investigation of the effect of ligand conformation on the redox properties of the corresponding PdII complexes. These Pd complexes adopt different conformations in solution, as supported by studies using variable scan rate, variable-temperature cyclic voltammetry (CV), differential pulse voltammety, and digital CV simulations at variable scan rates. The effect of the axial amine protonation on the spectroscopic and electrochemical properties of the complexes was also investigated. A number of new PdIII complexes were characterized by electron paramagnetic resonance, UVvis spectroscopy, and X-ray diffraction including [((tBu)N4)(PdCl2)-Cl-III]ClO4, a dicationic [((tBu)N4)(PdMe)-Me-III(MeCN)](OTf)(2), and an unstable tricationic [((tBu)N4)Pd-III(EtCN)(2)](3+) species. Although the electron-rich neutral complexes ((tBu)N4)PdMeCl and ((tBu)N4)PdMe2 are present in solution as a single isomer with the axial amines not interacting with the metal center, their low oxidation potentials are due to the presence of a minor conformer in which the (tBu)N4 ligand adopts a tridentade (kappa(3)) conformation. In addition, the redox properties of the ((tBu)N4)Pd complexes show a significant temperature dependence, as the low-temperature behavior is mainly due to the contribution from the major, most stable conformer, while the room-temperature redox properties are due to the formation of the minor, more easily oxidized conformer(s) with the (tBu)N4 ligand acting as a tridentate (kappa(3)) or tetradentate (kappa(4)) ligand. Overall, the coordination to the metal center of each axial amine donor of the tBuN4 ligand leads to a lowering of the Pd-II/(III) oxidation potential by similar to 0.6 V. These detailed electrochemical studies can thus provide important insights into the design of new ligands that can promote Pd-catalyzed oxidation reactions employing mild oxidants such as O-2.

  DOI：

  10.1021/ic5023054
• 作为产物：
  描述：

  chloro(N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane)(methyl)palladium(II) 以 not given 为溶剂， 生成 (N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IICl₂
  参考文献：
  名称：

  二氮杂吡啶并的中性和阳离子钯（II）配合物。结构，流动性和对乙烯的反应性

  摘要：

  钯复合物（吨-Bu-N 4）的PdCl 2（1），（吨-Bu-N 4）PdMeCl（2），（吨-Bu-N 4）PDME（NCMe）+ BAR 4 - （3），和（吨-Bu-N 4）PDME（C 2 H ^ 4）+巴4 - （4）[吨-Bu-N 4 = ñ，ñ “-ditertiobutyl-2,11二氮杂[3.3]（2,6- ）吡啶oph，Ar = 3,5-（CF 3）2 -C 6 H 3 ]已合成，并通过VT 1 H NMR和X射线（用于1和3）分析进行了表征。大环配体仅是双齿或三齿的，两种配位模式在溶液中共存于1和3。阳离子甲基-乙烯络合物4通过将乙烯插入Pd-Me键中而容易分解，因此排除了使用1（在MAO存在下）或3作为催化剂进行乙烯聚合。配合物1，3和4是fluxional，所述吨-Bu-N 4配体经历一个η 2 -η 3个振荡过程（Δ ģ ⧧ = 14.1-14.9摩尔千卡-1）

  DOI：

  10.1021/om010475e
• 作为试剂：
  描述：

  2-chloro-4-iodo-3-methoxypyridine 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 (N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IICl₂ 、 sodium carbonate 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 1.0h， 生成 1-(4-(2-(3-(4-(tert-butyl)piperazin-1-yl)phenyl)-3-methoxypyridin-4-yl)-2-chlorophenyl)-3-methyl-1,3-dihydro-2H-imidazol-2-one
  参考文献：
  名称：

  TREATMENT OF MYELOPROLIFERATIVE DISEASES AND DISORDERS WITH INHIBITORS OF BET FAMILY BDII BROMODOMAIN

  摘要：

  Disclosed are methods of treating myeloproliferative neoplasms, diseases, and disorders.

  公开号：

  WO2024124000A1