(triphenylphosphine)2Pt(1,3-dithiole-2-thione-4,5-dithiolate) | 96042-55-6

• 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: (triphenylphosphine)2Pt(1,3-dithiole-2-thione-4,5-dithiolate)
• 英文别名: (PPh3)2Pt(1,3-dithiole-2-thione-4,5-dithiolate)；Pt(PPh3)2(C3S5)
• CAS: 96042-55-6
• 化学式: C₃₉H₃₀P₂PtS₅
• 分子量: 916.025
• InChiKey: FQYCCTNDPWLSRH-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.24
• 重原子数：
  47.0
• 可旋转键数：
  8.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  4,5-Bis(benzoylthio)-1,3-dithiol-2-one 、 cis-dichlorobis(triphenylphosphine)platinum(II) 在 NaOCH₃ 作用下， 以 甲醇 为溶剂， 生成 (triphenylphosphine)2Pt(1,3-dithiole-2-thione-4,5-dithiolate)
  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

• Platinum(II) Complexes Bearing a Thiolate/Thioether Ligand – Hemilability vs. Dealkylation
  作者：Fabrice Guyon、Michael Knorr、Aurélie Garillon、Carsten Strohmann

  DOI：10.1002/ejic.201100943

  日期：2012.1

  abstraction of the chloro ligand of 2 by excess TlPF6. An S-demethylation reaction occurs when 1 is heated in acetonitrile to yield the structurally-characterised dithiolene complex [Pt(PEt3)2(dmit)] (5) (dmit2– = 2-thioxo-1,3-dithiole-4,5-dithiolate) and MeL. Treatment of cis-[Pt(PPh3)2Cl2] with 2 equiv. of L leads to a mixture of [Pt(PPh3)2(dmit)] (6) and [Pt(PPh3)(η1-L)(η2-L)] (7). Complex 7 predominates

  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
• The synthesis and characterization of platinum monodithiolene complexes containing 1,3-dithiole-2-oxo-4,5-dithiolate (dmid2−) and 1,3-dithiole-2-thione-4,5-dithiolate (dmit2−)
  作者：Christopher E. Keefer、Suzanne T. Purrington、Robert D. Bereman、Brian W. Knight、Danny R. Bedgood、Paul D. Boyle

  DOI：10.1016/s0020-1693(98)00244-8

  日期：1998.11

  X-ray crystal structures are also reported. 2: orthorhombic, Cmcm, a = 10.8535(6), b = 16.8503(7), c = 7.3622(3)A, Z = 4, 3: triclinic, P 1 ¯ , a = 11.2051(4), b = 11.4409(5), c = 15.2212(9)A, α = 71.882(4), β = 73.125(4), γ = 84.589(6)°, Z = 2. 4·CHCl 3 : triclinic, P 1 ¯ , a = 10.2521(5), b = 13.9387(14), c = 15.6884(18)A, α = 67.154(9), β = 89.380(15), γ = 83.570(13)°, Z = 2. The crystal structure

  单二硫代铂络合物（COD）Pt（dmid）（1），（COD）Pt（dmit）（2），（Ph 3 P）2 Pt（dmid）（3）和（Ph 3 P）2 Pt（dmit） （4）（其中COD = 1.5-环辛二烯，dmid = 1,3-二硫代-2-氧代-4,5-二硫代酸酯，dmit = 1,3-二硫代-2-硫代-4,5-二硫代酸酯）和特点。我们在这里报告其1 H NMR，195 Pt NMR，UV-Vis光谱和电化学。还报道了X射线晶体结构。2：斜方晶，Cmcm，a = 10.8535（6），b = 16.8503（7），c = 7.3622（3）A，Z = 4，3：三斜晶，P 1，a = 11.2051（4），b = 11.4409 （5），c ＝ 15.2212（9）A，α＝ 71.882（4），β＝ 73.125（4），γ＝ 84.589（6）°，Z ＝ 2。4·CHCl 3：三斜晶，P 1，a
• 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).