(bmmp-dmed)Ni | 581776-71-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (bmmp-dmed)Ni
• 英文别名: 2-methyl-1-[methyl-[2-[methyl-(2-methyl-2-sulfidopropyl)amino]ethyl]amino]propane-2-thiolate;nickel(2+)
• CAS: 581776-71-8；691001-11-3
• 化学式: C₁₂H₂₆N₂NiS₂
• 分子量: 321.174
• InChiKey: OSBIKKJEJSYDGP-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 、 (bmmp-dmed)Ni 以 乙腈 为溶剂， 以74%的产率得到((acetamide)2-N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine)NiI2
  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：

  bis(acetylacetonate)nickel(II) 、 N,N'-bis-2-methyl-mercaptopropyl-N,N'-dimethylethylenediamine 以 甲苯 为溶剂， 以45.7%的产率得到(bmmp-dmed)Ni
  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

文献信息

• Characterization of Steric and Electronic Properties of NiN₂S₂ Complexes as S-Donor Metallodithiolate Ligands
  作者：Marilyn V. Rampersad、Stephen P. Jeffery、Melissa L. Golden、Jonghyuk Lee、Joseph H. Reibenspies、Donald J. Darensbourg、Marcetta Y. Darensbourg

  DOI：10.1021/ja055051g

  日期：2005.12.1

  The physical properties and structures of a series of six complexes of the type (NiN(2)S(2))W(CO)(4) have been used to establish electronic and steric parameters for square planar NiN(2)S(2) complexes as bidentate, S-donor ligands. According to the nu(CO) stretching frequencies and associated computed Cotton-Kraihanzel force constants of the tungsten carbonyl adducts, there is little difference in

  一系列六种 (NiN(2)S(2))W(CO)(4) 配合物的物理性质和结构已被用于建立方形平面 NiN(2)S(2) 的电子和空间参数) 复合物作为双齿 S 供体配体。根据 nu(CO) 拉伸频率和相关计算的 Cotton-Kraihanzel 力常数的钨羰基加合物，该系列中五个中性 NiN(2)S(2) 金属二硫醇配体的供体能力几乎没有差异。双离子 Ni(ema)(2)(-) (ema = N,N'-ethylenebis(2-mercaptoacetamide)) 复合物将更多的电子密度转移到 W(CO)(4) 部分。供体能力排名以及与经典双齿配体的比较如下：Ni(ema)(=) > [NiN(2)S(2)](0)} > bipy大约 phen > Ph(2)PCH( 2)CH(2)PPh(2) > Ph(2)PCH(2)PPh(2)。来自循环伏安法的电化学数据发现 (NiN(2)S(2))W(CO)(4)
• Structural Analogues of the Bimetallic Reaction Center in Acetyl CoA Synthase:  A Ni−Ni Model with Bound CO
  作者：Rachel C. Linck、Cameron W. Spahn、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/ja035606c

  日期：2003.7.1

  Models for the active site of the acetyl CoA synthase (ACS) were synthesized by attachment of Cu+ and Ni(0) to nickel diaminodithiolate (S2N2) and diamidodithiolate (S2N2') complexes. The Ni-Ni species form stable CO adducts, i.e., [(CO)2Ni}NiS2N2'}]2-, whereas the Cu-NiS2N2 and Cu-NiS2N2' models do not. These results provide supporting evidence for a biological role for reduced nickel in ACS.