Pt(PEt3)2(C3S5) | 1358954-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: Pt(PEt3)2(C3S5)
• CAS: 1358954-68-3
• 化学式: C₁₅H₃₀P₂PtS₅
• 分子量: 627.761
• InChiKey: PWXKMNMOZKOVCD-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  23.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  trans-Pt(PEt3)2(C3S5CH3)2 以 乙腈 为溶剂， 以54%的产率得到Pt(PEt3)2(C3S5)
  参考文献：
  名称：

  带有硫醇盐/硫醚配体的铂 (II) 配合物 - Hemilability 与脱烷基化

  摘要：

  顺式-[Pt(PEt3)2Cl2] 的氯配体被 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate (L) 取代导致硫醇络合物反式-[Pt(PEt3)2ClL] (2) 和 trans-[Pt(PEt3)2L2] (1)，它们已通过 X 射线晶体学表征。在固态下，方形平面排列被 L 的环内硫原子覆盖，这分别导致 2 和 1 的扭曲的方形锥体和伪八面体几何形状。复合物 1 与 [Pt(PEt3)(η1-L)(η2-L)] (3) 在溶液中共存，这是由一种磷烷配体的可逆解离产生的。η1-(thiolato) 和 η2-(thiolato/thioether) L 在 3 中的组合已通过变温 1H NMR 光谱和晶体结构测定确定。在 cis-[Pt(PEt3)2L]+ (4) 中也观察到 L 的 η2-配位模式，这是由于过量的 TlPF6 提取了 2 的氯配体。当

  DOI：

  10.1002/ejic.201100943

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).