[Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)Br]Br | 179076-12-1

• 英文名称: [Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)Br]Br
• CAS: 179076-12-1
• 化学式: Br*C₄₂H₄₂BrP₄Pd
• 分子量: 936.919
• InChiKey: XAMSDSCSVDLURJ-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：

  [Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)Br]Br 、 三甲氧基磷 以 氯仿 为溶剂， 生成 [Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)(trimethylphosphite)](2+)
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ic9601596
• 作为产物：
  描述：

  potassium tetrabromopalladate(II) 、 三[2-(二苯基磷)乙基]磷 以 氯仿 、 水 、 乙腈 为溶剂， 以75%的产率得到[Pd(tris-(2-(diphenylphosphino)ethyl)phosphine)Br]Br
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ic9601596