cis-bis(4-pyridyldiphenylphosphine) palladium(II) methyl chloride | 673485-02-4

• 英文名称: cis-bis(4-pyridyldiphenylphosphine) palladium(II) methyl chloride
• CAS: 673485-02-4
• 化学式: C₃₅H₃₁ClN₂P₂Pd
• 分子量: 683.465
• InChiKey: HWJSPYHDFQKVHP-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：

  zinc tetraphenylporphyrin 、 cis-bis(4-pyridyldiphenylphosphine) palladium(II) methyl chloride 以 氘代氯仿 为溶剂， 生成 bis(4-pyridyldiphenylphosphine zinc(II) tetraphenylporphyrin) palldium(II) methyl chloride
  参考文献：
  名称：

  Encapsulation of Transition Metal Catalysts by Ligand-Template Directed Assembly

  摘要：

  Encapsulated transition metal catalysts are presented that are formed by templated self-assembly processes of simple building blocks such as porphyrins and pyridylphosphine and phosphite ligands, using selective metal-ligand interactions. These ligand assemblies coordinate to transition metals, leading to a new class of transition metal catalysts. The assembled catalyst systems were characterized using NMR and UV-vis spectroscopy and were identified under catalytic conditions using high-pressure infrared spectroscopy. Tris-3-pyridylphosphine binds three mesophenyl zinc(II) porphyrin units and consequently forms an assembly with the phosphorus donor atom completely encapsulated. The encapsulated phosphines lead exclusively to monoligated transition metal complexes, and in the rhodium-catalyzed hydroformylation of 1-octene the encapsulation of the catalysts resulted in a 10-fold increase in activity. In addition, the branched aldehyde was formed preferentially (l/b = 0.6), a selectivity that is highly unusual for this substrate, which is attributed to the encapsulation of the transition metal catalysts. An encapsulated rhodium catalyst based on ruthenium(II) porphyrins and tris-meta-pyridyl phosphine resulted in an even larger selectivity for the branched product (l/b = 0.4). These encapsulated catalysts can be prepared easily, and various template ligands and porphyrins, such as tris-3-pyridyl phosphite and ruthenium(l I) porphyrins, have been explored, leading to catalysts with different properties.

  DOI：

  10.1021/ja0386795
• 作为产物：
  描述：

  二苯基(吡啶-4-基)膦 、 chloromethyl(1,5-cyclooctadiene)palladium(II) 以 甲苯 为溶剂， 以82%的产率得到cis-bis(4-pyridyldiphenylphosphine) palladium(II) methyl chloride
  参考文献：
  名称：

  Encapsulation of Transition Metal Catalysts by Ligand-Template Directed Assembly

  摘要：

  Encapsulated transition metal catalysts are presented that are formed by templated self-assembly processes of simple building blocks such as porphyrins and pyridylphosphine and phosphite ligands, using selective metal-ligand interactions. These ligand assemblies coordinate to transition metals, leading to a new class of transition metal catalysts. The assembled catalyst systems were characterized using NMR and UV-vis spectroscopy and were identified under catalytic conditions using high-pressure infrared spectroscopy. Tris-3-pyridylphosphine binds three mesophenyl zinc(II) porphyrin units and consequently forms an assembly with the phosphorus donor atom completely encapsulated. The encapsulated phosphines lead exclusively to monoligated transition metal complexes, and in the rhodium-catalyzed hydroformylation of 1-octene the encapsulation of the catalysts resulted in a 10-fold increase in activity. In addition, the branched aldehyde was formed preferentially (l/b = 0.6), a selectivity that is highly unusual for this substrate, which is attributed to the encapsulation of the transition metal catalysts. An encapsulated rhodium catalyst based on ruthenium(II) porphyrins and tris-meta-pyridyl phosphine resulted in an even larger selectivity for the branched product (l/b = 0.4). These encapsulated catalysts can be prepared easily, and various template ligands and porphyrins, such as tris-3-pyridyl phosphite and ruthenium(l I) porphyrins, have been explored, leading to catalysts with different properties.

  DOI：

  10.1021/ja0386795

文献信息

• Rigid bis-zinc(ii) salphen building blocks for the formation of template-assisted bidentate ligands and their application in catalysis
  作者：Mark Kuil、P. Elsbeth Goudriaan、Arjan W. Kleij、Duncan M. Tooke、Anthony L. Spek、Piet W. N. M. van Leeuwen、Joost N. H. Reek

  DOI：10.1039/b702375h

  日期：——

  salphen template with two identical binding sites was studied. Using UV-vis, NMR-spectroscopy and X-ray analysis the formed structures were unambiguously proven. The application of these templated bidentate ligands in transition metal catalysis showed, in most cases, typical bidentate character. Compared to previous work based on a more flexible bis-zinc(II) porphyrin template, the current catalytic data

  研究了在具有两个相同结合位点的刚性双锌（II）连字模板上通过两个单齿吡啶基磷配体的选择性自组装，模板诱导的螯合双齿配体的形成。使用紫外可见光，核磁共振波谱和X射线分析可以清楚地证明所形成的结构。在大多数情况下，这些模板化的双齿配体在过渡金属催化中的应用显示出典型的双齿特征。相比基于一个更灵活的双-锌（以前的工作II）卟啉模板，电流催化数据表明，模板的刚性不是所施加的反应条件下的区域选择性和对映选择性的改善的重要因素。
• Thermodynamic Characterization of the Self-Assembly Process of a Three Component Heterobimetallic Bisporphyrin Macrocycle
  作者：Almudena González-Álvarez、Antoni Frontera、Pablo Ballester

  DOI：10.1021/jp9053742

  日期：2009.8.20

  The molecular self-assembly of macrocycle 4 is induced by the simultaneous coordination of two molecules of 4-pyridyldiphenylphosphine 3, a highly selective ditopic ligand, to Zn-bisporphyrin 1 and a square-planar Pd(II) complex 2·COD. We report a detailed thermodynamic characterization of the assembly process based on the quantification of each one of the two metal(Zn,Pd)-ligand(N,P) pairwise binding

  大环4的分子自组装是由高选择性的双位配体4-吡啶基二苯基膦3的两个分子与Zn-双卟啉1和方形Pd（II）配合物2 · COD的同时配位诱导的。我们报告了详细的热力学表征基于超分子大环中涉及的两个金属（Zn，Pd）-配体（N，P）的成对结合相互作用中的每一个的定量及其有效摩尔值（EM）。成对的金属-配体相互作用的实验值已经从参考模型系统的UV-vis，NMR滴定和等温滴定量热法实验中获得。反过来，EM = 1×10通过将为循环组装确定的实验总体稳定性常数与方程进行关联，以确定统计（非合作）自组装平衡常数，从而确定了-2 M。我们使用数值方法（SPECFIT程序）来预测三个分子的两种混合物的溶液行为（形态）1，3，和2 · COD在两个不同的浓度总体1相对于化学计量：以1：2。该方法使用了总的稳定性常数值和涉及4种多组分平衡自组装的11种物质（配合物）的化学计量。。统计地确定了某些物种的估计稳