Pd(1,2-bis(diphenylphosphanyl)ethane)(4-methylthio-2-thioxo-1,3-dithiole-5-thiolate₎₂ | 221296-97-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Pd(1,2-bis(diphenylphosphanyl)ethane)(4-methylthio-2-thioxo-1,3-dithiole-5-thiolate₎₂
• 英文别名: 2-diphenylphosphanylethyl(diphenyl)phosphane;5-methylsulfanyl-2-sulfanylidene-1,3-dithiole-4-thiolate;palladium(2+)
• CAS: 221296-97-5
• 化学式: C₃₄H₃₀P₂PdS₁₀
• 分子量: 927.64
• InChiKey: KQESJARXMGZMHS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  11.58
• 重原子数：
  47.0
• 可旋转键数：
  10.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  Pd(1,2-bis(diphenylphosphanyl)ethane)(4-methylthio-2-thioxo-1,3-dithiole-5-thiolate₎₂ 以 乙腈 为溶剂， 反应 6.0h， 生成 4,5-双(甲硫代)-1,3-二硫杂环戊烯-2-硫酮 、 Pd(η²-1,2-bis(diphenylphosphanyl)ethane)(dmit)
  参考文献：
  名称：

  PdII硫醇盐/硫醚配合物的CS键活化机理的实验和理论研究

  摘要：

  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).

  DOI：

  10.1021/acs.organomet.7b00039
• 作为产物：
  描述：

  1,2-二(二苯基膦基)乙烷二氯化钯(II) 、 cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate 以 丙酮 为溶剂， 反应 6.0h， 生成 Pd(1,2-bis(diphenylphosphanyl)ethane)(4-methylthio-2-thioxo-1,3-dithiole-5-thiolate₎₂
  参考文献：
  名称：

  PdII硫醇盐/硫醚配合物的CS键活化机理的实验和理论研究

  摘要：

  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).

  DOI：

  10.1021/acs.organomet.7b00039

文献信息

• Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate
  作者：S. Zeltner、R.-M. Olk、P. Jörchel、J. Sieler

  DOI：10.1002/(sici)1521-3749(199902)625:2<368::aid-zaac368>3.3.co;2-e

  日期：1999.2