chloro[tris(2-diphenylphosphinoethyl)phosphine]palladium(II) chloride | 85744-70-3

• 英文名称: chloro[tris(2-diphenylphosphinoethyl)phosphine]palladium(II) chloride
• 英文别名: [(tris[2-(diphenylphosphino)ethyl]phosphine)chloropalladium(II)] chloride；[Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)Cl]Cl；[Pd(II)Cl(tris[2-(diphenylphosphino)ethyl]phosphine)]Cl；[PdCl(tris[2-(diphenylphosphino)ethyl]phosphine)]Cl；[PdCl(pp3)]Cl；[(tris[2-(diphenylphosphino)ethyl]phosphine)chloropalladium(II)]chloride
• CAS: 85744-70-3；179076-11-0
• 化学式: C₄₂H₄₂ClP₄Pd*Cl
• 分子量: 848.017
• InChiKey: BREUFKRXELVUOX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  chloro[tris(2-diphenylphosphinoethyl)phosphine]palladium(II) chloride 、 sulfur 以 CHCl₃ 为溶剂， 生成 [Pd(II)Cl(tris[2-(diphenylphosphino)ethyl]phosphine disulfide)]Cl
  参考文献：
  名称：

  四齿和三齿膦配体在钯（II）上的逐步膦化硫化物形成和金属桥连反应

  摘要：

  三配位四齿膦配体[PdCl（pp 3）] Cl和[Pd（4-Cltp）（pp 3）]的五配位三方-双锥体Pd（II）配合物逐步形成膦硫化物的动力学研究。（BF 4）（pp 3 ＝三[2-（二苯基膦基）乙基]膦；进行4-Cltp ＝ 4-氯硫代苯酚酸酯），结果表明反应是通过具有侧链离解膦基的中间体进行的。中间体的形成用于在Pt（II）上的桥连反应，以形成膦桥接的直链三核和环状四核混合金属配合物。还报道了线性三齿膦（双[2-（二苯基膦基）乙基]苯基膦）和pp 3之间在膦基桥接反应中的空间转化机理的差异。

  DOI：

  10.1016/j.jorganchem.2010.02.006
• 作为产物：
  描述：

  在 六氯乙硅烷 作用下， 以 二氯甲烷 、 二氯甲烷-D2 为溶剂， 反应 0.58h， 生成 chloro[tris(2-diphenylphosphinoethyl)phosphine]palladium(II) chloride
  参考文献：
  名称：

  轻度一锅还原膦（III）及其金属催化剂上的膦（V）氧化物

  摘要：

  在温和的反应条件下，已经实现了使用草酰氯作为活化剂和六氯乙硅烷作为还原剂的一系列膦（V）氧化物的无金属还原。该方法成功地用于减少工业废物副产物三苯基膦（V）的氧化，关闭磷循环以干净地再生三苯基膦（III）。机理研究和量子化学计算支持中间体phospho盐的离解氯离子对乙硅烷硅的攻击，这是脱保护的限速步骤。

  DOI：

  10.1021/acs.organomet.0c00788

文献信息

• Stereoselective Preparation, Structures, and Reactivities of Phosphine-Bridged Mixed-Metal Trinuclear and Pentanuclear Complexes with Tris[2-(diphenylphosphino)ethyl]phosphine
  作者：Sen-ichi Aizawa、Kenji Saito、Tatsuya Kawamoto、Emi Matsumoto

  DOI：10.1021/ic060277l

  日期：2006.6.1

  pentanuclear complexes with Pd(II)-Pt(II)-Pd(II), Ni(II)-Pt(II)-Ni(II), and Rh(III)-Pd(II)-Pt(II)-Pd(II)-Rh(III) metal-ion sequences were almost quantitatively formed by the stepwise phosphine-bridging reaction of the terminal phosphino groups of tris[2-(diphenylphosphino)ethyl]phosphine (pp3), which is the tetradentate bound ligand of the starting Pd(II) and Ni(II) complexes. The solid-state structures

  磷化氢桥联的线性三核和五核配合物与Pd（II）-Pt（II）-Pd（II），Ni（II）-Pt（II）-Ni（II）和Rh（III）-Pd（II） -Pt（II）-Pd（II）-Rh（III）金属离子序列几乎是通过三[2-（二苯基膦基）乙基]膦（pp3）的末端膦基的逐步膦基桥接反应而定量形成的，它是起始Pd（II）和Ni（II）配合物的四齿结合配体。通过X射线结构分析确定三核配合物的固态结构，并通过NMR光谱表征溶液中的​​多核配合物的结构。三核和五核配合物的反式和顺式异构体，是由Pt（II）中心周围的几何结构产生的，只需改变起始配合物的抗衡阴离子即可有选择地获得：四氟硼酸盐[MX（pp3）]（BF4）[M = Pd（II）或Ni（II），X = Cl-或4-氯硫代苯酚盐（4-Cltp-）]，仅得到反式异构体，氯化物盐[PdCl（pp3）] Cl仅产生顺式异构体。具有4-Cltp-和氯配体，反式[[Pt（4-Cltp）2
• Rapid geometrical equilibrium of palladium(II) complexes with tris[2-(diphenylphosphino)ethyl]phosphine disulfide and diselenide and their catalytic activity for Suzuki coupling reaction
  作者：Sen-ichi Aizawa、Takashi Hase、Tsuyoshi Wada

  DOI：10.1016/j.jorganchem.2006.10.020

  日期：2007.1

  Palladium(II) complexes with a tetradentate pseudo-tripodal ligand having two phosphino groups and two phosphine sulfide or selenide groups, pp3X2 (pp3 = tris[2-(diphenylphosphino)ethyl]phosphine, X = S (1) or Se (2)), were prepared from [PdCl(pp3)]Cl. Both of these phosphine chalcogenide complexes 1 and 2 showed rapid equilibrium between the five-coordinate [PdCl(pp3X2)]Cl with two bound phosphine chalcogenide

  具有两个膦基和两个膦硫化物或硒化物基团的四齿假三脚形配体的钯（II）配合物，pp 3 X 2（pp 3  =三[2-（二苯基膦基）乙基]膦，X = S（1）或由[PdCl（pp 3）] Cl制备Se（2））。这两种膦硫属元素化物配合物1和2均显示具有两个结合膦硫属化物基团的五坐标[PdCl（pp 3 X 2）] Cl与四坐标[PdCl 2（pp 3 X 2）之间具有快速平衡）]，其中有两个在氯仿中解离的侧基。反应的热力学参数为[PdCl（pp 3 X 2）] + + Cl - ⇄[PdCl 2（pp 3 X 2）]，通过低温31 P NMR得出：K 298  = 3.7×10 3和5.4×10 2 摩尔-1，Δ ħ ∘  = 11.3±0.3和13.4±0.4千焦耳摩尔-1，Δ小号∘  = 106±2和97±2焦耳摩尔-1  ķ -1为1和2， 分别。1处246.7 K处的几何变化速率明显
• P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres
  作者：Helmuth Wachtler、Walter Schuh、Karl-Hans Ongania、Holger Kopacka、Klaus Wurst、Paul Peringer

  DOI：10.1039/b201709a

  日期：2002.6.7

  The complexes [M(η4-PP3)Cl]Cl (M = Ni, Pd or Pt, PP3 = P(CH2CH2PPh2)3) were treated with the metal based nucleophiles [Pt(PPh3)2(C2H4)], [Pt(η2-bicyclo(2.2.1)hept-2-ene)3] or [Pd2(dba)3] (dba = dibenzylideneacetone) to produce PP3 bridged metal–metal bonded homo- and heterodinuclear complexes in which the central and one terminal phosphorus of the PP3 ligand are chelated to one metal whilst the other two terminal phosphorus atoms bridge to the second metal centre. The products are characterised by 31P and 195Pt NMR spectroscopy; X-ray crystal structures were determined for [Pt2(PP3)(PPh3)Cl]Cl and [Pd2(PP3)Cl2].

  配合物 [M(η4-PP3)Cl]Cl（M = Ni、Pd 或 Pt，PP3 = P(CH2CH2PPh2)3）与金属基亲核物 [Pt(PPh3)2(C2H4)]、[Pt(η2-双环(2.2.1）庚-2-烯）3]或[Pd2（dba）3]（dba = 二亚苄基丙酮）来生成 PP3 桥接金属-金属键的同核和异核配合物，其中 PP3 配体的中心磷和一个末端磷与一种金属螯合，而另外两个末端磷原子则与第二种金属中心桥接。这些产物通过 31P 和 195Pt NMR 光谱进行表征；[Pt2(PP3)(PPh3)Cl]Cl 和 [Pd2(PP3)Cl2]的 X 射线晶体结构已经确定。
• Gray, Leslie R.; Gulliver, David J.; Levason, William, Journal of the Chemical Society, Dalton Transactions, 1983, p. 133 - 142
  作者：Gray, Leslie R.、Gulliver, David J.、Levason, William、Webster, Michael

  DOI：——

  日期：——
• Mechanistic Studies on Halo-Ligand Substitution of Five-Coordinate Trigonal-Bipyramidal Palladium(II) Complexes of Tris(2-(diphenylphosphino)ethyl)phosphine with Trimethyl Phosphite in Chloroform at Various Temperatures and Pressures
  作者：Sen-ichi Aizawa、Takashi Iida、Shigenobu Funahashi

  DOI：10.1021/ic9601596

  日期：1996.1.1

  Five-coordinate trigonal-bipyramidal palladium(II) complexes [Pd(pp(3))X]X (pp(3)=tris(2-(diphenylphosphino)ethyl)phosphine, X(-)=Cl-, Br-, I-) have been synthesized, and their structures in the solid state and in solution have been confirmed by X-ray crystal structure analysis and P-31 NMR spectroscopy, respectively. The P-31 NMR chemical shifts of the axial and equatorial phosphorus atoms indicate that the sigma- and pi-donating abilities of the axial monodentate ligands are in the order Cl- > Br- > I(-)much greater than P(OCH3)(3). The thermodynamic parameters for the equilibria between the halo complexes, [Pd(pp(3))Cl](+) + X(-)reversible arrow[Pd(pp(3))X](+) + Cl- (X(-)=Br-, I-), have been determined as follows: K-298=1.70, Delta H degrees=-5.66+/-0.07 kJ mol(-1), and Delta S degrees=-14.6+/-0.2 J K-1 mol(-1) for Br-; K-298=16.8, Delta H degrees=-16+/-1 kJ mol(-1), and Delta S degrees=-30+/-3 JK(-1) mol(-1) for I-. It is revealed that the relative stability of the halo complexes, I- > Br- > Cl- for the axial ligands, is determined by the difference in enthalpy. The second-order rate constants at 25 degrees C and activation parameters for the halo-ligand substitution with trimethyl phosphite, [Pd(pp(3))X](+) + P(OCH3)(3)-->[Pd(pp(3))(P(OCH3)(3))](2+) + X(-) (X(-)=Cl-, Br-, I-), have been obtained as follows: k(298)=1.19 x 10(-1) mol(-1) kg s(-1), Delta H double dagger=19+/-1 kJ mol(-1), Delta S double dagger=-198+/-3 J K-1 mol(-1), and Delta V double dagger=-25.5+/-0.5 cm(3) mol(-1) at 302.5 K for X(-)=Cl-; k(298)=6.20 x 10(-2) mol(-1) kg s(-1), Delta H double dagger=23+/-3 kJ mol(-1), Delta S double dagger=191+/-3 J K-1 mol(-1), and Delta V double dagger=-24.5+/-0.7 cm(3) mol(-1) at 302.5 K for X(-)=Br-; k(298)=1.09 x 10(-2) mol(-1) kg s(-1), Delta H double dagger=57+/-4 kJ mol(-1), Delta S double dagger=-89+/-15 J K-1 mol(-1), and Delta V double dagger=-22.6+/-0.8 cm(3) mol(-1) at 302.9 K for X(-)=I-. The associative mechanism is proposed on the basis of the kinetic behavior and the activation parameters. The kinetic properties an discussed in terms of the electronic properties of the axial and entering ligands.