Zn(S2C2(CO2Me)2)(N,N,N',N'-tetramethylethylenediamine) | 162557-44-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Zn(S2C2(CO2Me)2)(N,N,N',N'-tetramethylethylenediamine)
• 英文别名: [Zn(tmeda)(S2C2(COOMe)2)]；zinc;(Z)-1,4-dimethoxy-1,4-dioxobut-2-ene-2,3-dithiolate;N,N,N',N'-tetramethylethane-1,2-diamine
• CAS: 162557-44-0
• 化学式: C₁₂H₂₂N₂O₄S₂Zn
• 分子量: 387.84
• InChiKey: GGQIQPAUYMDUGR-LWFKIUJUSA-L

计算性质

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

• 作为反应物：
  描述：

  双(乙腈)氯化钯(II) 、 Zn(S2C2(CO2Me)2)(N,N,N',N'-tetramethylethylenediamine) 以 乙腈 为溶剂， 以52%的产率得到[Pd(C₂S₂(COOCH₃)2)]6
  参考文献：
  名称：

  [PdS₂C₂(COOMe)₂]₆ⁿ (n = 0, −1, −2, −3, −4):  Hexanuclear Homoleptic Palladium Dithiolene Complexes

  摘要：

  Reaction of a stoichiometric equivalent of the zinc-dithiolene complex, (tmeda)ZnS2C2(COOMe)2 (tmeda = tetramethylethylenediamine), with (MeCN)2PdCl2 results in a 1:1 homoleptic dithiolene that forms the hexanuclear cluster [PdS2C2(COOMe)2]6 (1). X-ray structure analysis of 1 indicates a Pd6S12 core comprised of six face-centered palladium atoms and 12 edge-centered sulfur atoms situated on an imaginary approximate cube. Complex 1 undergoes four distinct and reversible one-electron redox steps in dichloromethane at -186, -484, -1174, and -1524 mV versus a standard calomel electrode (ferrocenium+/ferrocene redox couple 409 mV). The two-electron reduction product of 1, [Bu4N]2[(PdS2C2(COOMe)2)6] (2), has been chemically isolated and characterized.

  DOI：

  10.1021/ja026079k
• 作为产物：
  描述：

  四甲基乙二胺 以 四氢呋喃 为溶剂， 生成 Zn(S2C2(CO2Me)2)(N,N,N',N'-tetramethylethylenediamine)
  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

文献信息

• 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).