trans-[Pd(COOCH3)(H2O)(PPh3)2](p-toluenesulfonate) | 530112-06-2

• 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: trans-[Pd(COOCH3)(H2O)(PPh3)2](p-toluenesulfonate)
• 英文别名: trans-[Pd(COOMe)(H2O)(PPh3)2](TsO)；trans-[Pd(COOCH3)(H2O)(PPh3)2]TsO
• CAS: 530112-06-2
• 化学式: C₇H₇O₃S*C₃₈H₃₅O₃P₂Pd
• 分子量: 879.258
• InChiKey: URANAZAAAJIKOV-UHFFFAOYSA-M

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：

  trans-[Pd(COOCH3)(H2O)(PPh3)2](p-toluenesulfonate) 以 甲醇 、 丙醇 、 异丙醇 为溶剂， 生成 trans-[Pd(COO-n-Pr)(H2O)(PPh3)2](TsO)
  参考文献：
  名称：

  新型碳烷氧基双（三苯基膦）钯（II）阳离子配合物：乙烯的合成，表征，反应性及其在催化碳氢烷氧基化中的作用。反式-[Pd（COOMe）（TsO）（PPh 3）2 ]·2CHCl 3的X射线结构

  摘要：

  阳离子络合物的反式- [钯（COOR）（H 2 O）（PPH 3）2 ]（TSO）已经通过反应而合成顺式- [钯（H 2 O）2（PPH 3）2 ]（TSO）2 · 2H 2 O与RO中的CO（R = Me和Et），实际上在室温下，或通过反式-[Pd（COOMe）Cl（PPh 3）2 ]与Ag（TsO）的数学交换（R =  n -Pr ，iso -Pr，n -Bu，iso -Bu，sec -Bu）。它们具有IR的特点，1 H NMR和31 P NMR光谱。

  DOI：

  10.1016/j.molcata.2008.10.002
• 作为产物：
  描述：

  甲醇 、 trans-[Pd(COO-n-Pr)(H2O)(PPh3)2](TsO) 以 甲醇 为溶剂， 生成 trans-[Pd(COOCH3)(H2O)(PPh3)2](p-toluenesulfonate)
  参考文献：
  名称：

  新型碳烷氧基双（三苯基膦）钯（II）阳离子配合物：乙烯的合成，表征，反应性及其在催化碳氢烷氧基化中的作用。反式-[Pd（COOMe）（TsO）（PPh 3）2 ]·2CHCl 3的X射线结构

  摘要：

  阳离子络合物的反式- [钯（COOR）（H 2 O）（PPH 3）2 ]（TSO）已经通过反应而合成顺式- [钯（H 2 O）2（PPH 3）2 ]（TSO）2 · 2H 2 O与RO中的CO（R = Me和Et），实际上在室温下，或通过反式-[Pd（COOMe）Cl（PPh 3）2 ]与Ag（TsO）的数学交换（R =  n -Pr ，iso -Pr，n -Bu，iso -Bu，sec -Bu）。它们具有IR的特点，1 H NMR和31 P NMR光谱。

  DOI：

  10.1016/j.molcata.2008.10.002

文献信息

• Synthesis, characterization and X-ray structure of trans-[Pd(COOCH3)(H2O)(PPh3)2](TsO), a possible intermediate in the catalytic hydroesterification of olefins (TsO=p-toluenesulfonate)
  作者：Gianni Cavinato、Andrea Vavasori、Luigi Toniolo、Franco Benetollo

  DOI：10.1016/s0020-1693(02)01187-8

  日期：2003.1

  The complex trans-[Pd(COOCH3)(H2O)(PPh3)(2)](TsO) (I) has been synthesized by reacting trans-[Pd(COOCH3)Cl(PPh3)(2)] with AgTsO in methanol. It has been characterized by IR, H-1 and P-31 NMR spectroscopy. Crystals of trans-[Pd(COOCH3)(H2O)(PPh3)(2)](TsO). (.) (CH3OH) (II) have been obtained by re-crystallization of I in methanol. The structure of the complex has been determined by X-ray analysis. It shows a slightly distorted square planar conformation around the central palladium. The coordinated water molecule and the clathrated methanol form a contact with the uncoordinated TsO- anion, suggesting hydrogen bond interaction. Since I is a possible intermediate in the catalytic hydroesterification of olefins, its catalytic activity in the hydroesterification of ethylene has been tested at 100 degreesC under 45 atm of a 1/1 mixture of ethylene and CO in methanol as solvent, also in the presence of PPh3 and TsOH. Without addition of PPh3 and TsOH, I affords to traces of methylpropionate together with Pd(0) complexes and Pd metal. The same results are obtained when complex I is tested in the presence of PPh3, except that in this case formation of palladium metal is avoided. Using the system I/PPh3/TsOH = 1/6/8, a TOF (mol of ester/mol Pd*h) of 1800 h(-1) is obtained. We propose that the role of the acid TsOH is to favor the formation of a Pd-hydride intermediate and/or to reactivate the Pd(0) species, stabilized by the excess of PPh3, via an oxidative addition of the acid. Since the acid does not favor the formation of Pd-alkoxy species we suggest that complex I plays only a minor role in catalysis and that this occurs via a Pd-hydride species. (C) 2002 Elsevier Science B.V. All rights reserved.