cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate | 221296-23-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate
• 英文别名: cesium 1,3-dithiole-2-thioxo-4-methylthio-5-thiolate；caesium 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate；Cesium 5-methylsulfanyl-2-thioxo-1,3-dithiole-4-thiolate；cesium;5-methylsulfanyl-2-sulfanylidene-1,3-dithiole-4-thiolate
• CAS: 221296-23-7
• 化学式: C₄H₃S₅*Cs
• 分子量: 344.303
• InChiKey: OASDSIHFJNRHKG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.17
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  109
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate 在 双氧水 、 sodium iodide 作用下， 以 水 为溶剂， 反应 24.0h， 以40%的产率得到4-Methylsulfanyl-5-[(5-methylsulfanyl-2-sulfanylidene-1,3-dithiol-4-yl)disulfanyl]-1,3-dithiole-2-thione
  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：

  4-benzoylthio-5-methylthio-1,3-dithiole-2-thione 在 cesium hydroxide 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 0.02h， 以54%的产率得到cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate
  参考文献：
  名称：

  铸币金属硫醚-硫醇配合物的合成及晶体结构

  摘要：

  铜 (I)、银 (I) 和两种 (Ph3P)nM(L) [n = 1, 2, 3; L = 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate (La), 1,2-dicyano-1-(methylthio)ethene-2-thiolate (Lb)] 已经合成。这些配合物的分子结构由 X 射线晶体学确定，并显示出这些 (Ph3P)nM(L) 配合物的配位硫原子和配位几何结构的差异。在 (Ph3P)2Cu(L) (2) 中，硫醚硫醇盐配体作为双齿配体，而在银和金配合物 (Ph3P)3Ag(L) (3) 和 (Ph3P)2Au(L) (4) 中，只有硫醇硫被配位。(Ph3P)2Au(La) (4a) 的磷烷配体之一在沸腾的丙酮中发生解离，得到线性双配位金 (I) 中心 (Ph3P)Au(La) (5a)。

  DOI：

  10.1002/1099-0682(200106)2001:6<1535::aid-ejic1535>3.0.co;2-p

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
• New tetrathiafulvalenes containing a 2,5-bis(thiophen-2-yl)pyrrole fragment: Synthesis, optical properties, and electrochemical behavior
  作者：E. A. Ignatenko、E. V. Shklyaeva、G. G. Abashev

  DOI：10.1134/s107042801309025x

  日期：2013.9

  The reaction of 1-(3-bromopropyl)-2,5-bis(thiophen-2-yl)-1H-pyrrole with cesium 5-methylsulfanyl-2-thioxo-1,3-dithiole-4-thiolate generated in situ gave previously unknown 4-3-[2,5-bis(thiophen-2-yl)-1H-pyrrol-1-yl]propylsulfanyl}-5-methylsulfanyl-1,3-dithiole-2-thione, and cross-coupling of the latter with 4,5-disubstituted 1,3-dithiole-2-thiones in the presence of triethyl phosphite afforded new substituted tetrathiafulvalenes containing a 2,5-bis(thiophen-2-yl)pyrrole fragment. Optical properties and electrochemical behavior of the synthesized compounds were studied, and their ability to undergo electropolymerization was confirmed.
• 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