(TMEDA)Zn(S6) | 162557-46-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 有机二硫化物
• 英文名称: (TMEDA)Zn(S6)
• CAS: 162557-46-2
• 化学式: C₆H₁₆N₂S₆Zn
• 分子量: 373.992
• InChiKey: DUXPVJMWKYUWBR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (TMEDA)Zn(S6) 以 neat (no solvent) 为溶剂， 生成 zinc sulfide
  参考文献：
  名称：

  Donor Solvent Mediated Reactions of Elemental Zinc and Sulfur, sans Explosion

  摘要：

  The reactions of zinc powder with solutions of elemental sulfur in various donor solvents is described. Complexes of the type ZnS6(N-donor)(2) are obtained for the ligands tetramethylethylenediamine (TMEDA), N-methylimidazole (MeIm), and 4-(N,N-dimethylamino)pyridine (DMAP). Ligand competition studies on pyridine solutions revealed that the relative stability constants (DMAP > MeIm > TMEDA > pyridine) parallel the basicity of the ligands. The TMEDA complex crystallizes in the monoclinic space group C2/c with a = 12.255(3) Angstrom, b = 10.559(2) Angstrom, c = 12.392(2) Angstrom, and beta = 110.22(2)degrees. In the solid state ZnS6(TMEDA) adopts a tetrahedral geometry with a seven-membered ZnS6 ring. A variety of reactivity studies were conducted on ZnS6(TMEDA). Solutions of ZnS6(TMEDA) undergo Ligand exchange with quinuclidine and MeIm to afford ZnS(6)L(2) (L = MeLm, quinuclidine). The anionic species [ZnS12](2-) is formed upon addition of (PPh(4))(2)S-6 to ZnS6(TMEDA). Optical and reactivity studies showed that MeIm, but not pyridine, displaces the polysulfide from ZnS6(MeIm)(2) as indicated by the appearance of the chromophore S-3(-). ZnS6(TMEDA) reacts with the electrophilic acetylenes dimethyl acetylenedicarboxylate and methyl propiolate to give the dithiolene complexes ZnS(2)C(2)Ri(CO(2)Me)(TMEDA) {R = CO(2)Me, H}. Solid ZnS6(TMEDA) cleanly decomposes at 350 degrees C as indicated by TGA studies. Preparative scale conversions at 500 degrees C affords cubic ZnS. Submicron cubic ZnS is generated upon partial desulfurization of ZnS6(TMEDA) with tertiary phosphines as established by electron microscopic studies.

  DOI：

  10.1021/ic00115a038
• 作为产物：
  描述：

  四甲基乙二胺 在 sodium methylate 作用下， 以 甲醇 、 氯苯 为溶剂， 反应 2.0h， 生成 (TMEDA)Zn(S6)
  参考文献：
  名称：

  [EN] PROCESSES USEFUL IN THE MANUFACTURE OF CYCLODODECASULFUR
  [FR] PROCÉDÉS UTILES DANS LA FABRICATION DE CYCLODODÉCASULFURE

  摘要：

  公开了生产十二硫环的方法，包括以下步骤：将溴化物与分子氯反应以获得分子溴和氯化物；在水溶液中氧化氯化物并去除电子以获得分子氯；用电子还原水以获得氢和氢氧化物；将金属硫衍生物与分子溴反应，以产生十二硫环和金属溴化物衍生物。

  公开号：

  WO2020185483A1
• 作为试剂：
  描述：

  1,2-benzenebis(sulfenyl chloride) 在 (TMEDA)Zn(S6) 作用下， 以 二硫化碳 为溶剂， 反应 1.0h， 以60%的产率得到1,2,3,4,5,6,7-benzooctathiecin
  参考文献：
  名称：

  Preparation of Organic Polysulfanes R2Sn (n = 5, 7, 8, 9) from Sulfenyl Chlorides, RSCl, and Transition Metal Polysulfido Complexes

  摘要：

  DOI：

  10.1002/(sici)1099-0682(200005)2000:5<921::aid-ejic921>3.0.co;2-2

文献信息

• A New Allotrope of Elemental Sulfur: Convenient Preparation ofcyclo-S14 from S8
  作者：Ralf Steudel、Oliver Schumann、Jürgen Buschmann、Peter Luger

  DOI：10.1002/(sici)1521-3773(19980918)37:17<2377::aid-anie2377>3.0.co;2-o

  日期：1998.9.18

  Three simple steps lead from S8 to cyclo-S14 , which is stable at 20°C. The final synthetic step [Eq. (a)] provides the title compound, which was characterized spectroscopically and by X-ray structure analysis. Formally, the structure of S14 is derived by insertion of an S2 unit into S12 . tmeda=N,N,N',N'-tetramethylethylenediamine.

  从S 8到环S 14只需三个简单步骤，该步骤在20°C稳定。最后的合成步骤 [（a）]提供标题化合物，其通过光谱法和X-射线结构分析表征。正式地，通过将S 2单元插入S 12来获得S 14的结构。tmeda ＝ N，N，N′，N′-四甲基乙二胺。
• Dehydrogenative Route to Metallo Dithiolenes:  The Reaction of Zinc Polysulfides and Alkenes
  作者：Robert J. Pafford、Jun-Hong Chou、Thomas B. Rauchfuss

  DOI：10.1021/ic990090c

  日期：1999.8.1

  Complexes of the type ZnS6(TMEDA), ZnS4(PMDETA), and ZnS4(Me(3)TACN) react with electrophilic alkenes to give dithiolene complexes ZnS2C2R2(amine)(n). The Me(3)TACN complex is the most reactive, while the more conveniently prepared PMDETA complex also undergoes this reaction at useful rates. The following alkenes were successfully tested: C2H2(CO2Me)(2) (cis and trans isomers), C2H3(CO2Me), C2H3(CN), 1,2-C2H2Me(CN), C2H3(CHO), and 1,2-C2H2(CN)(Ph). Crystallographic analysis shows that the highly reactive complex ZnS4(Me(3)TACN) is structurally similar to ZnS4(PMDETA), including the presence of an elongated Zn-N-ax bond. Model studies indicate that the reaction of alkenes with LnZnSx proceeds via the reversible formation of a dipolar intermediate, as indicated by the ability of the polysulfido complexes to catalyze the isomerization of cis-C2H2(CO2Me)(2). It is proposed that such dipolar species undergoes ring closure to give alkanedithiolato intermediates, e.g., Zn[S2C2H2(CO2Me)(2)](PMDETA). The dithiolato complexes Zn[S2C2H2(CO2Me)(2)](PMDETA) and Zn[S2C2H2(CO2Me)(2)](TMEDA) were prepared from ZnMe2, the di- and triamines, and the dithiol meso-(HS)(2)C2H2(CO2Me)(2). These dithiolates undergoes dehydrogenation upon treatment with S-8 to give the dithiolene Zn[S2C2(CO2Me)(2)]L-n at a rate that is independent of the ancillary ligand L. The dithiolene ligands can be removed from the Zn center by treatment with [COCl2](3) and Cp2TiCl2; in this way Zn[S2C2H(CN)](PMDETA) was converted to OCS2C2H(CN) and Cp2TiS2C2H(CN).
• Chalcogenospecific Synthesis of 1,2-Se2S6 Using ZnS6(TMEDA)
  作者：Atul K. Verma、Thomas B. Rauchfuss

  DOI：10.1021/ic00128a035

  日期：1995.11

  The recently reported hexasulfido complex ZnS6(TMEDA) is a potent polysulfide transfer agent as demonstrated by its ability to convert (C5H5)(2)TiCl2 into (C5H5)(2)-TiS5. More interesting is the use of the zinc complex to transfer an intact. S-6 Unit as established with the ''chalcogenospecific'' synthesis of 1,2-Se2S6. 1,2-Se2S6 is a rare example of easily prepared stable sulfur selenide available in isomeric purity.
• Pafford, Robert J.; Rauchfuss, Thomas B., Inorganic Chemistry, 1998, vol. 37, # 8, p. 1974 - 1980
  作者：Pafford, Robert J.、Rauchfuss, Thomas B.

  DOI：——

  日期：——