[Pd(C6H4(CH2NH2)-2)(μ-OAc)]2 | 152507-01-2

• 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)(μ-OAc)]2
• 英文别名: palladium(2+);phenylmethanamine;diacetate
• CAS: 152507-01-2；196202-54-7
• 化学式: C₁₈H₂₂N₂O₄Pd₂
• 分子量: 543.224
• InChiKey: XTOYVYDKKXOKOU-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：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Pd(C6H4(CH2NH2)-2)(μ-OAc)]2 、 三苯基膦 以 二氯甲烷 为溶剂， 以75%的产率得到[Pd(C6H4(CH2NH2)-2)(OAc)(PPh3)]
  参考文献：
  名称：

  乙酸钯（II）对单，二和三苄胺的环钯缩合：苄胺氮原子周围的体积对内部金属化的影响

  摘要：

  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

  DOI：

  10.1016/s0022-328x(98)01156-5
• 作为产物：
  描述：

  bisacetatobisbenzylaminepalladium(II) 以 二氯甲烷 、 乙腈 为溶剂， 生成 [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

文献信息

• The cyclopalladation reaction of benzylamine revisited
  作者：Joan Albert、Jaume Granell、Raquel Tavera

  DOI：10.1016/s0277-5387(02)01338-4

  日期：2003.1

  (μ-OAc)2[Pd(3-DC6H3CH2NH2)]2 were obtained when benzylamine and palladium(II) acetate in a one-to-one molar were treated in monodeuterated acetic acid (DOAc) at 60 °C for 24 h. These mixtures were isolated in yields of 10–30% and deuterium contents in the range between 0.7 and 0.9. Furthermore, the treatment of benzylamine and palladium(II) acetate in a one-to-one molar ratio under reflux of glacial

  苄胺和乙酸钯（II）在甲苯或冰醋酸中以1：1的摩尔比在60°C下反应24小时，生成了乙酰胺桥联的苄胺（μ-OAc）2的环钯二聚体[Pd（ C 6 H 4 CH 2 NH 2）] 2（1）的产率分别为40–75％和20–40％。此外，化合物的混合物1，1D1式[（3-DC 6 ħ 3 CH 2 NH 2）的Pd]（μ-OAC）2 [的Pd（C 6 H ^ 4 CH 2 NH 2）]和1d2的式（μ-OAc）2 [Pd（3-DC 6 H 3 CH 2 NH 2）] 2通过一对一摩尔的苄胺和乙酸钯（II）进行单氘处理得到。乙酸（DOAc）在60°C下放置24小时。分离出这些混合物，产率为10％至30％，氘含量在0.7到0.9之间。此外，苄胺和钯（II）乙酸盐溶于下冰醋酸回流45分钟一对一的摩尔比处理产生的乙酸根桥接内切-cyclopalladated苄基苄基胺的二聚体（μ-OAC）2 [钯（C 6
• Domino Oxidative [Pd]-Catalysis: One-Pot Synthesis of Fluorenones Starting from Simple Benzylamines and Iodo Arenes
  作者：Devarapalli Ravi Kumar、Gedu Satyanarayana

  DOI：10.1021/acs.orglett.5b03077

  日期：2015.12.4

  fluorenones is presented. The overall reaction proceeds through the formation of a five membered Pd(II)-cycle via a highly regioselective ortho C(sp2)-H activation(s) of simple benzylamine that combines with external iodo arenes to give ortho arylated products. Significantly, the reaction further activates the C(sp3)-H and C(sp2)-H (intramolecular oxidative Heck coupling) bonds to give tricyclic imine systems

  提出了有效合成芴酮的多米诺[Pd]-催化。整个反应通过简单苄基胺的高区域选择性邻位C（sp 2）-H活化与外部碘代芳烃结合而形成的五元Pd（II）循环来进行，从而得到邻芳基化产物。显着地，该反应进一步活化了C（sp 3）-H和C（sp 2）-H（分子内氧化性Heck偶联）键以产生三环亚胺系统。然后，通常的水处理提供了稠合的三环酮（芴酮）。值得注意的是，此一锅操作可有效构建两个C至C至三个C至C键
• Second- and inverse order pathways in the mechanism of orthopalladation of primary amines
  作者：Sergey A Kurzeev、Gregory M Kazankov、Alexander D Ryabov

  DOI：10.1016/s0020-1693(02)01148-9

  日期：2002.11

  The orthopalladation of benzylamine (baH) by Pd(II) acetate in acetonitrile occurs in two time-resolved steps. A first faster step taking place at 25 degreesC results in the formation of the N-bound complex [Pd(OAc)(2)(baH)(2)] and follows a second-order kinetics in the incoming amine according to the rate law k(obs) = k(1)[baH](2). The second order in baH arises from the successive substitution of the solvent in [Pd(OAc)(2)(MeCN)(2)]. The latter complex transforms slowly into the orthometalated derivative [Pd(ba)(OAc)](2) at 60 degreesC. The initial rate of this step is inversely proportional to the concentration of baH and the following rate law holds: V, = k(m)[Pd(II)](t)/[baH]. This is accounted for in terms of the mechanism involving a reversible dissociation of one baH ligand from [Pd(OAc)(2)(baH)(2)] followed by the electrophilic C-H bond cleavage of N-bound baH by Pd(II). (C) 2002 Elsevier Science B.V. All rights reserved.