| 145447-62-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 145447-62-7
• 化学式: C₆H₁₅ClNPPdS₂
• 分子量: 338.171
• InChiKey: YUSXJIYWTQYEMC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.08
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  以 四氢呋喃 、 氘代甲苯 为溶剂， 生成 (dimethyldithiocarbamato)isopropyl(trimethylphosphine)palladium(II)
  参考文献：
  名称：

  （Me2NCS2）Pd（PR3）（烷基）配合物中烷基配体的异构化。烷基中杂原子取代基对烷基异构化平衡和烷基金属配合物稳定性的影响

  摘要：

  A series of complexes of unusually stable alkylpalladium complexes of the formula (Me2NCS2)Pd(PR3) (alkyl) (R = Me, Et) have been prepared from the reaction of (Me2NCS2)Pd(PR3)CI and the appropriate alkyllithium or Grignard reagent. The substituted complexes Me2NCS2)Pd(PEt3)(CH2CH2CF3) and (Me2NCS2)Pd(PEt3)(CH2CH2CN) were prepared in similar reactions, and the isomer of the latter, (Me2NCS2)Pd(PEt3)(CH(CN)CH3), was prepared from the low-temperature, in situ reaction of (Me2NCS2)Pd(PEt3)H and CH2CHCN. The reaction of (Me2NCS2)Pd(PEt3)Cl with Li[C(CH3)3]CuCN gives a color change indicative of the formation of the alkylpalladium complex, but this tert-butyl compound decomposes above -40-degrees-C with the formation of its isomer, (Me2NCS2)Pd(PEt3)(CH2CH(CH3)2). With this one exception, all of these complexes are extremely stable, especially the substituted alkyl complexes, which can be heated over 100-degrees-C in solution for extended periods without noticeable decomposition. Heating the unsubstituted isomers at 75-degrees-C in solution leads to isomerization of the alkyl ligand. For example, heating either (Me2NCS2)Pd(PEt3)(CH2CH2CH3) or (Me2NCS2)Pd(PEt3)(CH(CH3)2) leads to a 10:1.0 equilibrium mixture, respectively, of the two. An equilibrium mixture of 10:1.0 is found for the other alkyl ligands studied. This 1.6 kcal/mol difference between the isomers is proposed to be the difference in energy between secondary versus primary alkylmetal complexes in the absence of steric constraints imposed by other ligands in the coordination sphere. At 120-degrees-C, the primary isomer (Me2NCS2)Pd(PEt3)(CH2CH2CN) isomerizes completely to the secondary isomer (Me2NCS2)Pd(PEt3)(CH(CN)CH3), whereas (Me2NCS2)Pd(PEt3) (CH2CH2CF3) isomerizes to a 1:1 mixture with its secondary isomer. The alkyl ligand in (Me2NCS2)Pd(PEt3)(CH(CH3)2) exchanges with 1-hexene to yield an isomeric mixture of all three (Me2NCS2)Pd(PEt3)(hexyl) isomers. This reaction is only successful for monosubstituted alkenes. Kinetic studies of the alkyl isomerization reaction show that it is first order and that Lewis bases, especially added PEt3, substantially slow the reaction. It has also been shown that the free and complexed PEt3 exchange rapidly. The structure of ((CH2)4NCS2)Pd(PEt3)(CH(CN)CH3) has been determined by X-ray crystallography. Crystal data: triclinic, P1BAR, a = 11.865 (3) angstrom, b = 16.003 (5) angstrom, c = 10.060 (3) angstrom, alpha = 93.45 (3)-degrees, beta = 91.27 (3)-degrees, gamma = 101.08 (3)-degrees, V = 1870 angstrom3, Z = 4, R(F) = 4.1 %, and R(wF) = 5.8%. There are no obvious structural features in the standard square planar geometry of this compound that indicate why the cyanide substituent stabilizes this branched isomer in favor of the linear isomer.

  DOI：

  10.1021/om00060a054