trans-PdEt(OAc)(PMe3)2 | 157565-69-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: trans-PdEt(OAc)(PMe3)2
• CAS: 157565-69-0
• 化学式: C₁₀H₂₆O₂P₂Pd
• 分子量: 346.683
• InChiKey: MJFWZNCPMCDHLJ-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-PdEt(OAc)(PMe3)2 在 sodium chloride 作用下， 以 二氯甲烷 、 水 为溶剂， 以50-70的产率得到trans-Pd(ethyl)Cl(trimethylphosphine)2
  参考文献：
  名称：

  Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes, EtPd(X)(PMe3)2 (X = Electronegative Ligands)

  摘要：

  A series of monoethylpalladium complexes coordinated with various electronegative ligands, trans-[PdEt(X)(PMe(3))(2)], where X = OPh (2a), O2CCH3 (2b), O2CCH2Cl (2c), O2CCHCl2 (2d), O2CCl3 (2e), O2CCH2CH=CH2 (2f), SPh (2g), SCOCH3 (2h), Cl (2i), Br (2j), and I (2k) have been prepared by protonolysis of trans-PdEt(2)(PMe(3))(2) with HX or by metathesis of the known monoethylpalladium acetate complex. These complexes were characterized by means of H-1-, 13C{1H}-, and (31)p{H-1}-NMR, IR, and elemental analysis. Complexes 2a and 2b are thermolyzed in solution with evolution of ethylene whereas complexes 2c-2e and 2g-2k are decomposed with evolution of ethylene and ethane, Kinetic studies on the thermolysis of the ethylpalladium complexes revealed that they decompose according to the first-order rate law in concentration of the palladium complexes. The thermolysis is hindered by addition of X(-) to the solution. A detailed analysis of the thermolysis revealed that there are two thermolysis routes, one major route involving dissociation of the X ligand to generate an unstable cationic ethylpalladium species that is rapidly thermolyzed, evolving ethylene, and another minor route proceeding from the neutral complex without dissociation of the anionic ligand. Comparison of the rate constant k(1) for dissociation of the anionic ligand X from trans-PdEt(X)(PMe(3))(2) showed that k(1) is the smallest for the Cl- ligand dissociation. Activation parameters for the dissociation of the acetate ligand from 2b were found as follows: Delta H double dagger = 9.9(+/-1) kcal/mol, Delta S double dagger = -41(+/-2) cal/(K.mol). The large negative entropy is consistent with a mechanism where dissociation of X is assisted by solvent coordination to generate a solvent-coordinated cationic ethylpalladium complex susceptible to beta-H elimination. In fact removal of the chloride ligand on treatment of trans-PdEt(Cl)(PMe(3))(2) with AgBF4 gave a thermally unstable complex trans-[PdEt(solvent)(PMe(3))2](BF4-)-B-+ which is readily decomposed to liberate ethylene above -30 degrees C.

  DOI：

  10.1021/om00021a027
• 作为产物：
  描述：

  trans-PdEt2(PMe3)2 在 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以70.3%的产率得到trans-PdEt(OAc)(PMe3)2
  参考文献：
  名称：

  Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes, EtPd(X)(PMe3)2 (X = Electronegative Ligands)

  摘要：

  A series of monoethylpalladium complexes coordinated with various electronegative ligands, trans-[PdEt(X)(PMe(3))(2)], where X = OPh (2a), O2CCH3 (2b), O2CCH2Cl (2c), O2CCHCl2 (2d), O2CCl3 (2e), O2CCH2CH=CH2 (2f), SPh (2g), SCOCH3 (2h), Cl (2i), Br (2j), and I (2k) have been prepared by protonolysis of trans-PdEt(2)(PMe(3))(2) with HX or by metathesis of the known monoethylpalladium acetate complex. These complexes were characterized by means of H-1-, 13C{1H}-, and (31)p{H-1}-NMR, IR, and elemental analysis. Complexes 2a and 2b are thermolyzed in solution with evolution of ethylene whereas complexes 2c-2e and 2g-2k are decomposed with evolution of ethylene and ethane, Kinetic studies on the thermolysis of the ethylpalladium complexes revealed that they decompose according to the first-order rate law in concentration of the palladium complexes. The thermolysis is hindered by addition of X(-) to the solution. A detailed analysis of the thermolysis revealed that there are two thermolysis routes, one major route involving dissociation of the X ligand to generate an unstable cationic ethylpalladium species that is rapidly thermolyzed, evolving ethylene, and another minor route proceeding from the neutral complex without dissociation of the anionic ligand. Comparison of the rate constant k(1) for dissociation of the anionic ligand X from trans-PdEt(X)(PMe(3))(2) showed that k(1) is the smallest for the Cl- ligand dissociation. Activation parameters for the dissociation of the acetate ligand from 2b were found as follows: Delta H double dagger = 9.9(+/-1) kcal/mol, Delta S double dagger = -41(+/-2) cal/(K.mol). The large negative entropy is consistent with a mechanism where dissociation of X is assisted by solvent coordination to generate a solvent-coordinated cationic ethylpalladium complex susceptible to beta-H elimination. In fact removal of the chloride ligand on treatment of trans-PdEt(Cl)(PMe(3))(2) with AgBF4 gave a thermally unstable complex trans-[PdEt(solvent)(PMe(3))2](BF4-)-B-+ which is readily decomposed to liberate ethylene above -30 degrees C.

  DOI：

  10.1021/om00021a027