[Pd(acetate)(μ-acetate)(C6H5CH2NH2)]2 | 187818-89-9

• 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: [Pd(acetate)(μ-acetate)(C6H5CH2NH2)]2
• 英文别名: [Pd(OAc)(μ-OAc)(PhCH2NH2)]2；[Pd(acetate)(μ-acetate)(C₆H₅CH₂NH₂)]₂
• CAS: 187818-89-9
• 化学式: C₂₂H₃₀N₂O₈Pd₂
• 分子量: 663.329
• InChiKey: GYLYJFJRGIKLFA-UHFFFAOYSA-J

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：

  [Pd(acetate)(μ-acetate)(C6H5CH2NH2)]2 以 乙腈 为溶剂， 以49%的产率得到[Pd(C6H4(CH2NH2)-2)(μ-OAc)]2
  参考文献：
  名称：

  Orthometalation of Primary Amines. 4.¹ Orthopalladation of Primary Benzylamines and (2-Phenylethyl)amine

  摘要：

  By the refluxing of an acetonitrile solution of [Pd(OAc)(2)](3) and primary amines 4-XC(6)H(4)CH(2)NH(2) (F, Cl, NO2, OMe), 3,5-X(2)C(6)H(3)CH(2)NH(2) (X = OMe), or PhCH(2)CH(2)NH(2) (Pd:amine = 1:1) and subsequent addition of excess NaBr, the corresponding orthometalated complexes [Pd{C6H3(CH2NH2)-2,X-5}(mu-Br)](2), [Pd{C6H3(CH2NH2)-2,(OMe)(2)-4,6}(mu-Br)](2), or [Pd{C6H3(CH2NH2)-2}(mu-Br)](2) are obtained. Alternatively, the hydrochloride of 4-XC(6)H(4)CH(2)NH(2) (X = F, NO2) can also be used to prepare the corresponding [Pd{C6H3(CH2NH2)-2,X-5}(mu-Cl)](2) complexes. These results show that primary benzylamines can be orthometalated even if the substituents are electron-withdrawing groups and that 2-(phenyl)ethylamine can be orthometalated in spite of the six-membered ring that it forms. These reactions occur via intermediate complexes [Pd(OAc)(2)L(2)], which react with [Pd(OAc)(2)](3) to give the dimeric species [Pd(OAc)(mu-OAc)L](2) (L = amine), from which in turn the orthometalated complexes are formed. Each of these steps has been studied, and both types of intermediates have been isolated for all the amines. PPh(3) reacts with the orthometalated complexes to give the corresponding products of the bridge splitting. The crystal structures of [Pd(OAc)(mu-OAc)L](2) (L = 4-O2NC6H4CH2NH2) and [Pd{C6H4(CH2CH2NH2)-2}Br(PPh(3))] have been determined by X-ray diffraction.

  DOI：

  10.1021/om9609574
• 作为产物：
  描述：

  苄胺 以 二氯甲烷 、 丙酮 为溶剂， 生成 [Pd(acetate)(μ-acetate)(C6H5CH2NH2)]2
  参考文献：
  名称：

  Orthometalation of Primary Amines. 4.¹ Orthopalladation of Primary Benzylamines and (2-Phenylethyl)amine

  摘要：

  By the refluxing of an acetonitrile solution of [Pd(OAc)(2)](3) and primary amines 4-XC(6)H(4)CH(2)NH(2) (F, Cl, NO2, OMe), 3,5-X(2)C(6)H(3)CH(2)NH(2) (X = OMe), or PhCH(2)CH(2)NH(2) (Pd:amine = 1:1) and subsequent addition of excess NaBr, the corresponding orthometalated complexes [Pd{C6H3(CH2NH2)-2,X-5}(mu-Br)](2), [Pd{C6H3(CH2NH2)-2,(OMe)(2)-4,6}(mu-Br)](2), or [Pd{C6H3(CH2NH2)-2}(mu-Br)](2) are obtained. Alternatively, the hydrochloride of 4-XC(6)H(4)CH(2)NH(2) (X = F, NO2) can also be used to prepare the corresponding [Pd{C6H3(CH2NH2)-2,X-5}(mu-Cl)](2) complexes. These results show that primary benzylamines can be orthometalated even if the substituents are electron-withdrawing groups and that 2-(phenyl)ethylamine can be orthometalated in spite of the six-membered ring that it forms. These reactions occur via intermediate complexes [Pd(OAc)(2)L(2)], which react with [Pd(OAc)(2)](3) to give the dimeric species [Pd(OAc)(mu-OAc)L](2) (L = amine), from which in turn the orthometalated complexes are formed. Each of these steps has been studied, and both types of intermediates have been isolated for all the amines. PPh(3) reacts with the orthometalated complexes to give the corresponding products of the bridge splitting. The crystal structures of [Pd(OAc)(mu-OAc)L](2) (L = 4-O2NC6H4CH2NH2) and [Pd{C6H4(CH2CH2NH2)-2}Br(PPh(3))] have been determined by X-ray diffraction.

  DOI：

  10.1021/om9609574

文献信息

• A kinetico-mechanistic study on the C–H bond activation of primary benzylamines; cooperative and solid-state cyclopalladation on dimeric complexes
  作者：Helena Font、Mercè Font-Bardia、Kerman Gómez、Gabriel González、Jaume Granell、Israel Macho、Manuel Martínez

  DOI：10.1039/c4dt01463d

  日期：——

  The cyclometallation reactions of dinuclear μ-acetato complexes of the type [Pd(AcO)(μ-AcO)L]2 (L = 4-RC6H4CH2NH2, R = H, Cl, F, CF3), a process found to occur readily even in the solid state, have been studied from a kinetico-mechanistic perspective. Data indicate that the dinuclear acetato bridged derivatives are excellent starting materials to activate carbon–hydrogen bonds in a facile way. In all

  [Pd（AcO）（μ-AcO）L] 2型（L = 4-RC 6 H 4 CH 2 NH 2，R = H，Cl，F，CF 3），从动力学-力学的角度研究了即使在固态下也容易发生的过程。数据表明，双核乙酰桥联衍生物是出色的起始材料，可以轻松地激活碳氢键。在所有情况下，均已证明可以通过协调的乙酰基配体建立起一致的歧义质子抽象。还发现金属化作用以协同方式发生，其中二聚配合物的第一钯单元的金属化作用是决定速率的。在任何过程中均未观察到任何中间单金属化合物。完全由C–H键激活后获得的动力学上有利的双环钯化合物与最终分离的XRD表征的复合物不符。该物种具有经典的开本二聚体形式，