[Pd(C6H4(CH2NH2)-2)(OAc)(PPh3)] | 187819-03-0

• 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: [Pd(C6H4(CH2NH2)-2)(OAc)(PPh3)]
• CAS: 187819-03-0
• 化学式: C₂₇H₂₆NO₂PPd
• 分子量: 533.903
• InChiKey: OKEUUJLGFFUTPU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  66.15
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  苄胺 以 二氯甲烷 、 乙腈 为溶剂， 生成 [Pd(C6H4(CH2NH2)-2)(OAc)(PPh3)]
  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

• Cyclopalladation of mono-, di- and tribenzylamine by palladium(II) acetate
  作者：Yoshio Fuchita、Kazuhiko Yoshinaga、Tomoko Hanaki、Hiroyuki Kawano、Junko Kinoshita-Nagaoka

  DOI：10.1016/s0022-328x(98)01156-5

  日期：1999.5

  dibenzylamine complex [Pd(O2CMe)2(PhCH2)2NH}2] has been converted into a cyclopalladated complex. The reactivity of the three benzylamines towards cyclopalladation has been discussed in terms of the co-ordinating ability influenced by the bulkiness around the nitrogen atom. Temperature-dependent 1H-NMR spectra are observed for mononuclear cyclopalladated complexes [Pd(O2CMe)C6H4CH2N(CH2Ph)2–C1, N}L] (L=PPh3

  通过使相应的胺与等摩尔量的乙酸钯（II）反应（反应i）或加热相应的双胺络合物[Pd（O 2 CME）2 （PhCH 2）n NH 3- n } 2 ]（n = 1，2）（反应ii）。通过反应i，所有三种胺都经历环钯。然而，在反应ii的情况下，仅二苄胺络合物[Pd（O 2 CME）2 （PhCH 2）2 NH}2 ]已经转化为环钯配合物。关于三种苄胺对环钯的反应性，已根据受氮原子周围的松密度影响的配位能力进行了讨论。温度依赖性1个H-NMR谱中观察到单核环钯配合物[钯（O 2 CME）C 6 H ^ 4 CH 2 N（CH 2 PH）2 - c ^ 1，  Ñ } L]（L = PPH 3，ASPH 3）并且归因于环palpalated螯合物环中氮原子的离解。杂合双环钯配合物[Pd [C 6ħ 4 CH 2 N（CH 2 PH）2 - c ^ 1，  Ñ ]（C 6 H ^ 4 CH