[Pd(C6H3(CH2NH2)-2,Cl-5)(μ-Br)]2 | 187818-96-8

• 英文名称: [Pd(C6H3(CH2NH2)-2,Cl-5)(μ-Br)]2
• CAS: 187818-96-8
• 化学式: C₁₄H₁₄Br₂Cl₂N₂Pd₂
• 分子量: 653.833
• InChiKey: SDTRUPWWBCQFGJ-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：
  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(C6H3(CH2NH2)-2,Cl-5)(μ-Br)]2 、 三苯基膦 以 二氯甲烷 为溶剂， 以76%的产率得到[Pd(C6H3(CH2NH2)-2,Cl-5)Br(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
• 作为产物：
  描述：

  对氯苄胺 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 生成 [Pd(C6H3(CH2NH2)-2,Cl-5)(μ-Br)]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

• Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C Bond of Ortho-palladated Primary and Secondary Arylalkylamines
  作者：José Vicente、Isabel Saura-Llamas、Juana Turpín、Delia Bautista、Carmen Ramírez de Arellano、Peter G. Jones

  DOI：10.1021/om9002895

  日期：2009.7.27

  (E)) react with RC≡CR (R = Et, Ph) to give [Pdκ2(C,N)-C(R)═C(R)C(R)═C(R)C6H3CH2NH2-2,X-5}Br] (X = Cl, R = Et (7a), Ph (7b); X = F, R = Et (8a), Ph (8b); X = NO2, R = Ph (9)) through a double insertion of the alkyne into the Pd−C bond. Complexes A and D react with PhC≡CCO2R in molar ratio 1:6−7 to afford a mixture of di-inserted head-to-tail and tail-to-tail isomers [Pdκ2(C,N)-C(R′)═C(R′′)C(Ph)═C(CO2

  的邻位金属化配合物[钯2 κ 2（C，N）-C 6 H ^ 4 CH 2 CH 2 NHMe-2} 2（μ-溴）2 ]（1）可通过一个回流1来制备：1混合物在乙腈中加入Pd（OAc）2和N-甲基苯乙胺，然后加入过量的NaBr。复杂1起反应以PPH 3，得到单核衍生物[钯κ 2（C ^，Ñ）-C 6 H ^ 4 CH 2 CH 2NHMe-2} Br（PPh 3）]（2）。阳离子络合物[钯κ 2（C ^，Ñ）-C 6 H ^ 4 CH 2 CH 2 NHMe-2}（PY）2 ] CLO 4（3）可通过反应而得到的1与AgClO 4和吡啶。先前报道的络合物[钯2 κ 2（C，N）-C 6 H ^ 4 CH 2 NHCH 2 PH-2} 2（μ-溴）2 ]（甲）反应与PhC≡CCO 2 R（R = ME等），得到monoinserted衍生物[钯2 κ 2（C ^，Ñ）-C（PH）= C（CO