Pd(η²-1,2-bis(diphenylphosphanyl)ethane)(dmit) | 96042-53-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Pd(η²-1,2-bis(diphenylphosphanyl)ethane)(dmit)
• 英文别名: 2-Diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);2-sulfanylidene-1,3-dithiole-4,5-dithiolate
• CAS: 96042-53-4
• 化学式: C₂₉H₂₄P₂PdS₅
• 分子量: 701.207
• InChiKey: VIVCPCBEQLLAFG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  84.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,2-二(二苯基膦基)乙烷二氯化钯(II) 、 4,5-Bis(benzoylthio)-1,3-dithiol-2-one 在 NaOCH₃ 作用下， 以 甲醇 为溶剂， 生成 Pd(η²-1,2-bis(diphenylphosphanyl)ethane)(dmit)
  参考文献：
  名称：

  Vicente, R.; Ribas, J.; Cassoux, P., Nouveau Journal de Chimie, 1984, vol. 8, p. 653 - 658

  摘要：

  DOI：

文献信息

• Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes
  作者：Sushil Kumar、Fabrice Guyon、Michael Knorr、Stéphane Labat、Karinne Miqueu、Christopher Golz、Carsten Strohmann

  DOI：10.1021/acs.organomet.7b00039

  日期：2017.4.10

  Two equivalents of L (L = 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate or Medmit) react with cis-Pd-(PR3)(2)Cl-2 (R = Ph and Et) to afford Pd(PR3)(eta(1)-L)(eta(2)-L) (R = Et: 1; R = Ph: 2) complexes, which have been characterized by X-ray crystallography. These compounds are dynamic in solution due to an exchange of the thiomethyl groups on palladium. Variable-temperature H-1 NMR spectroscopy reveals a low coalescence temperature (173 K). Treatment of Pd(diphos)Cl-2 (diphos = dppe or dppm) with 2 equiv of L affords thiolato complexes Pd(dppe)(eta(1)-L)(2) (3) and Pd(dppm)(eta(1)-L)(2) (4). Whereas 3 is rigid in solution with firm eta(2)-coordination of dppe and eta(1) coordinationof the thiolate, two linkage isomers Pd(eta(2)-dppm)(eta(1)-L)(2) and Pd(eta(1)-dppm)(eta(1)-L)(eta(2)-L) coexist in a solution of 4. L coordinated on Pd-II undergoes a S-demethylation reaction leading to dithiolene complexes and MeL. This transformation requires high temperature, and its efficiency depends on the nature of the phosphines as well as the nature of the metal (Pd vs Pt). DFT calculations reveal that the most likely mechanism depends on the lability of phosphines. Starting from M(PR3)(2)(eta(1)-L)(2) (M=Pd and Pt; R = Ph and Et), the favored sequence implies decoordination of one triethyl phosphine (M(PEt3)(eta(1)-L)(eta(2)-L)(2) as intermediate) or two triphenylphosphines (Pd(mu(2)-L)(2) as intermediate) followed by oxidative addition and reductive elimination (OA/RE) reactions. In the case of PEt3, this OA/RE sequence can also compete with an intramolecular nucleophilic addition (A(N)), which can be described as an attack of a thiolate sulfur atom on a CH3+ carbocation. An intramolecular S(N)2 process was found to be the most feasible, starting from M(dppe)(eta(1)-L)(2) (M= Pd and Pt), with the nucleophile approaching the thiomethyl group at an angle of 180 degrees with respect to the C-CH3-S bond. The influence of the coligand has also been studied experimentally. Structurally characterized disulfide L-L dimer has been isolated upon reaction of 2 equiv of L with MCl2 (M = Pd and Pt).
• Vicente, R.; Ribas, J.; Cassoux, P., Nouveau Journal de Chimie, 1984, vol. 8, p. 653 - 658
  作者：Vicente, R.、Ribas, J.、Cassoux, P.

  DOI：——

  日期：——