trans-Pd(S-DMSO)(O-DMSO)(TFA)₂ | 14654-75-2

• 英文名称: trans-Pd(S-DMSO)(O-DMSO)(TFA)₂
• 英文别名: trans-Pd(S-DMSO)(O-DMSO)(trifluoroacetate)₂；trans-(dimethyl sulfoxide-O)(dimethyl sulfoxide-S)bis(trifluoroacetato)palladium(II)；methylsulfinylmethane;palladium(2+);2,2,2-trifluoroacetate
• CAS: 14654-75-2
• 化学式: C₈H₁₂F₆O₆PdS₂
• 分子量: 488.722
• InChiKey: YXULYTOXQNVZEY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.42
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  153
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  Pd₃(TFA)₆ 、 二甲基亚砜 以 乙酸乙酯 为溶剂， 生成 trans-Pd(S-DMSO)(O-DMSO)(TFA)₂
  参考文献：
  名称：

  Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)₂(TFA)₂

  摘要：

  Recent studies have shown that Pd(DMSO)(2)(TFA)(2) (TFA = trifluoroacetate) is an effective catalyst for a number of different aerobic oxidation reactions. Here, we provide insights into the coordination of DMSO to palladium(II) in both the solid state and in solution. A crystal structure of Pd(DMSO)(2)(TFA)(2) confirms that the solid-state structure of this species has one O-bound and one S-bound DMSO ligand, and a crystallographically characterized mono-DMSO complex, trans-Pd(DMSO)(OH2)(TFA)(2), exhibits an S-bound DMSO ligand. H-1 and F-19 NMR spectroscopic studies show that, in EtOAc and THF-d(8), Pd(DMSO)(2)(TFA)(2) consists of an equilibrium mixture of Pd(S-DMSO)(O-DMSO)(TFA)2 and Pd(S-DMSO)2(TFA)2. The O-bound DMSO is determined to be more labile than the S-bound DMSO ligand, and both DMSO ligands are more labile in THF relative to EtOAc as the solvent. DMSO coordination to Pd-II is substantially less favorable when the TFA ligands are replaced with acetate. An analogous carboxylate ligand effect is observed in the coordination of the bidentate sulfoxide ligand, 1,2-bis(phenylsulfinyl)ethane to Pd-II. DMSO coordination to Pd(TFA)2 is shown to be incomplete in AcOH-d(4) and toluene-d(8), resulting in Pd-II/DMSO adducts with <2:1 DMSO/Pd-II stoichiometry. Collectively, these results provide useful insights into the coordination properties of DMSO to Pd-II under catalytically relevant conditions.

  DOI：

  10.1021/ic301799p
• 作为试剂：
  描述：

  spiro[4,5]decan-6-one-7-d₁ 在 trans-Pd(S-DMSO)(O-DMSO)(TFA)₂ 作用下， 以 乙酸乙酯 为溶剂， 反应 24.0h， 生成 spiro[4.5]dec-7-en-6-one 、
  参考文献：
  名称：

  Aerobic Dehydrogenation of Cyclohexanone to Cyclohexenone Catalyzed by Pd(DMSO)₂(TFA)₂: Evidence for Ligand-Controlled Chemoselectivity

  摘要：

  The dehydrogenation of cyclohexanones affords cyclohexenones or phenols via removal of 1 or 2 equiv of H-2, respectively. We recently reported several Pd-II catalyst systems that effect aerobic dehydrogenation of cyclohexanones with different product selectivities. Pd(DMSO)(2)(TFA)(2) is unique in its high chemoselectivity for the conversion of cyclohexanones to cyclohexenones, without promoting subsequent dehydrogenation of cyclohexenones to phenols. Kinetic and mechanistic studies of these reactions reveal the key role of the dimethylsulfoxide (DMSO) ligand in controlling this chemoselectivity. DMSO has minimal kinetic influence on the rate of Pd(TFA)(2)-catalyzed dehydrogenation of cyclohexanone to cyclohexenone, while it strongly inhibits the second dehydrogenation step, conversion of cyclohexenone to phenol. These contrasting kinetic effects of DMSO provide the basis for chemoselective formation of cyclohexenones.

  DOI：

  10.1021/ja4031648

文献信息

• Bancroft, Daniel P.; Cotton, F. Albert; Verbruggen, Mark, Acta Crystallographica, Section C: Crystal Structure Communications, 1989, vol. 45, p. 1289 - 1292
  作者：Bancroft, Daniel P.、Cotton, F. Albert、Verbruggen, Mark

  DOI：——

  日期：——