[Pd(bis(2-diphenylphosphinoethyl)phenylphosphine)(CF3SO3)](CF3SO3) | 169964-82-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [Pd(bis(2-diphenylphosphinoethyl)phenylphosphine)(CF3SO3)](CF3SO3)
• 英文别名: Bis(2-diphenylphosphanylethyl)-phenylphosphane;palladium(2+);trifluoromethanesulfonate
• CAS: 169964-82-3
• 化学式: CF₃O₃S*C₃₅H₃₃F₃O₃P₃PdS
• 分子量: 939.118
• InChiKey: UGMKVWZJGXAOJL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.16
• 重原子数：
  54
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (diphenylamino)(diphenylphosphino)methane 、 [Pd(bis(2-diphenylphosphinoethyl)phenylphosphine)(CF3SO3)](CF3SO3) 以 二氯甲烷 为溶剂， 以56%的产率得到
  参考文献：
  名称：

  Group 10 complexes containing phosphinomethylamine ligands: Synthesis, structural analysis and electrochemical studies

  摘要：

  The reaction of [M(triphos)OTf](OTf) (M = Pd, Pt; triphos = (Ph2PCH2CH2)(2)PPh; OTf = triflate) with one equivalent of a diphenylphosphinomethylamine ligand ((PNPh(R))-N-Ph2, R = Ph or Me) leads to the formation of the M(II) complexes [Pd(triphos)(PNPh(R))-N-Ph2](OTf)(2) (1a, R = Ph; 1b, R = Me) and [Pt(triphos)(PNPh(R))-N-Ph2](OTf)(2) (2a, R = Ph; 2b, R = Me). Complexes 1a, 1b, 2a and 2b were obtained in moderate yields and characterized by elemental analysis, H-1, C-13, P-31 NMR and X-ray diffraction. The redox behavior of these complexes shows a reversible reduction wave with half-wave potentials ranging from -1.04 to -1.23 V. Electrocatalytic proton reduction studies demonstrate these complexes function as hydrogen production catalysts with turn over frequencies ranging from 120 to 200 s (1). (C) 2011 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.07.001
• 作为产物：
  描述：

  silver trifluoromethanesulfonate 、 双(2-二苯基膦乙基)苯基磷 、 dichloro(cycloocta-1,5-diene)palladium (II) 以 二氯甲烷 为溶剂， 以85%的产率得到[Pd(bis(2-diphenylphosphinoethyl)phenylphosphine)(CF3SO3)](CF3SO3)
  参考文献：
  名称：

  钯催化的6-氨基己-1-炔的环化反应

  摘要：

  以6-氨基己-1-炔环合成2-甲基-1,2-脱氢哌啶为例，研究了钯催化炔烃加成胺的机理和限制因素。络合物[Pd（Triphos）]（CF 3 SO 3）2在一系列结构上和电子上不同的钯配合物中，具有最高的催化活性。几种方法，例如量热法和原位红外光谱和核磁共振光谱法，被用来获得可能的反应周期的证据。似乎（i）底物最初通过胺基团进行配位，并且（ii）形成了中间体，该中间体是胺对配位炔的亲核攻击的产物。向反应混合物中添加酸可导致反应速率显着提高，这可能是通过加速中间体复合物中钯-碳键的蛋白水解裂解来实现的。

  DOI：

  10.1021/om010524n

文献信息

• The role of protons in hydroamination reactions involving homogeneous and heterogeneous catalysts
  作者：J. Penzien、R.Q. Su、T.E. Müller

  DOI：10.1016/s1381-1169(01)00496-4

  日期：2002.5

  The addition of amines to CC double and triple bonds using different transition metal catalysts was investigated. Lewis acidic complexes of rhodium, palladium, copper and zinc are effective catalysts for the cyclisation of 3-aminopropyl-vinylether and 6-aminohex-1-yne. The catalytic activity of these homogeneous catalysts is significantly increased in the presence of catalytic amounts of Bronsted acids. The higher activity of corresponding heterogeneous catalysts, here shown for zinc ion exchanged beta zeolites, is probably related to residual protons in the material. The respective role played by Lewis acidic metal centres and protons in the catalytic systems is discussed. It is concluded that Bronsted and Lewis acids, and their respective properties, have to be taken into account in the rational design of hydroamination processes mediated by late transition metals. (C) 2002 Elsevier Science B.V. All rights reserved.
• Palladium-Catalyzed Cyclization of 6-Aminohex-1-yne
  作者：Thomas E. Müller、Michael Berger、Manja Grosche、Eberhardt Herdtweck、Franz P. Schmidtchen

  DOI：10.1021/om010524n

  日期：2001.10.1

  IR and NMR spectroscopy, were used to obtain evidence for a possible reaction cycle. It seems likely that (i) the substrate initially coordinates via the amine group and (ii) an intermediate is formed which is the product of a nucleophilic attack of the amine on a coordinated alkyne. Addition of an acid to the reaction mixture led to a strong increase in the reaction rate, probably by accelerating protolytic

  以6-氨基己-1-炔环合成2-甲基-1,2-脱氢哌啶为例，研究了钯催化炔烃加成胺的机理和限制因素。络合物[Pd（Triphos）]（CF 3 SO 3）2在一系列结构上和电子上不同的钯配合物中，具有最高的催化活性。几种方法，例如量热法和原位红外光谱和核磁共振光谱法，被用来获得可能的反应周期的证据。似乎（i）底物最初通过胺基团进行配位，并且（ii）形成了中间体，该中间体是胺对配位炔的亲核攻击的产物。向反应混合物中添加酸可导致反应速率显着提高，这可能是通过加速中间体复合物中钯-碳键的蛋白水解裂解来实现的。
• Group 10 complexes containing phosphinomethylamine ligands: Synthesis, structural analysis and electrochemical studies
  作者：Nolan W. Waggoner、Lindsay S. Spreer、Brian J. Boro、Daniel L. DuBois、Monte L. Helm

  DOI：10.1016/j.ica.2011.07.001

  日期：2012.1

  The reaction of [M(triphos)OTf](OTf) (M = Pd, Pt; triphos = (Ph2PCH2CH2)(2)PPh; OTf = triflate) with one equivalent of a diphenylphosphinomethylamine ligand ((PNPh(R))-N-Ph2, R = Ph or Me) leads to the formation of the M(II) complexes [Pd(triphos)(PNPh(R))-N-Ph2](OTf)(2) (1a, R = Ph; 1b, R = Me) and [Pt(triphos)(PNPh(R))-N-Ph2](OTf)(2) (2a, R = Ph; 2b, R = Me). Complexes 1a, 1b, 2a and 2b were obtained in moderate yields and characterized by elemental analysis, H-1, C-13, P-31 NMR and X-ray diffraction. The redox behavior of these complexes shows a reversible reduction wave with half-wave potentials ranging from -1.04 to -1.23 V. Electrocatalytic proton reduction studies demonstrate these complexes function as hydrogen production catalysts with turn over frequencies ranging from 120 to 200 s (1). (C) 2011 Elsevier B. V. All rights reserved.