Zn(N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine(2-)) | 690628-56-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: Zn(N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine(2-))
• 英文别名: (N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine(2-))Zn；zinc;2-methyl-1-[methyl-[2-[methyl-(2-methyl-2-sulfidopropyl)amino]ethyl]amino]propane-2-thiolate
• CAS: 690628-56-9
• 化学式: C₁₂H₂₆N₂S₂Zn
• 分子量: 327.874
• InChiKey: PCNCZWFFYJZILX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  8.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-碘乙酰胺 、 Zn(N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine(2-)) 以 乙腈 为溶剂， 以61%的产率得到((acetamide)2-N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine)ZnI2*2H2O
  参考文献：
  名称：

  Structural comparison of alkylated derivatives of (bmmp-dmed)Ni and (bmmp-dmed)Zn

  摘要：

  The sulfur-alkylation of the nickel (1) and zinc (2) complexes of the dithiolate N2S2 ligand N,N'-bis-2-methyl-mercaptopropyl- N,N'-dimethylethylenediamine, H-2(bmmp-dmed), have been investigated. Reactions with iodomethane yield [(Me-bmmp-dmed)Ni]PF6 (3), [(Me-2-bmmp-dmed)NiI2] (4), and [(Me-2-bmmp-dmed)ZnI](2)[ZnI4] (5). Addition of iodoacetamide yields [(AA(2)-bmmp-dmed)Ni]I-2 (6) and [(AA(2)-bmmp-dmed)Zn]I-2 (7). Each of the metal-thioether products (3-7) have been characterized spectroscopically and by X-ray crystallography. Structural data is compared with that of the previously reported thiolato precursors 1 and 2. Sulfur-alkylation of 1 results in small relative changes in the nickel-sulfur bond distance, whereas for 2, the zinc-sulfur bond distance increases significantly, but is not cleaved. The difference between nickel and zinc is attributed to the release of a pi*-bonding interaction between the metal and sulfur upon alkylation that compensates for the decreased a-donor ability of the thioether in the case of nickel. but not for zinc. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.09.035
• 作为产物：
  描述：

  zinc(II) chloride 、 N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine 在 NaH 作用下， 以 乙醇 为溶剂， 以30%的产率得到Zn(N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine(2-))
  参考文献：
  名称：

  Synthesis and Oxygenation of a Nickel(II) and Zinc(II) Dithiolate:  An Experimental and Theoretical Comparison

  摘要：

  The diamino-dithiolato N2S2 ligand N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine, H-2(bmmp-dmed), and its nickel (1) and zinc (2) complexes have been prepared and their reactivities with hydrogen peroxide investigated. Complex 1 yields a mixture of sulfenato (RSO-), 4, sulfinato (RSO2-) 3, and sulfonato (RSO3-), 5, products upon addition of H2O2. Products are separable by column chromatography. Stoichiometric addition of H2O2 to 2 yields an inseparable mixture. Excess peroxide addition results in oxygenation of the ligand to the disulfonate, 6, and decomplexation of zinc. Complexes 1, 2, and 3 and compound 6 have been investigated by X-ray crystallography, and their structures are reported. Density functional theory (DFT) calculations of 1 and 2 reveal significant sulfur p character in the HOMO of each complex. However, 1 also shows significant metal d character that is pi-antibonding with respect to the sulfur p orbitals. Complex 2 shows little metal character in the HOMO. Implications of the HOMO with respect to S-centered reactivity and metal ligand distances in S-oxygenated products are provided.

  DOI：

  10.1021/ic035205y