(N,N,N',N'-tetramethyl-1,2-ethanediamino)Mg(CD3)2 | 220135-38-6

• 分子结构分类: 有机化合物
• 英文名称: (N,N,N',N'-tetramethyl-1,2-ethanediamino)Mg(CD3)2
• 英文别名: (N,N,N',N'-tetramethylethylenediamine)Mg(CD3)2
• CAS: 220135-38-6
• 化学式: C₈H₂₂MgN₂
• 分子量: 176.533
• InChiKey: FVEQWZFIBQBVHF-SYOMHBRDSA-N

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：

  (N,N,N',N'-tetramethyl-1,2-ethanediamino)Mg(CD3)2 、 (N,N,N',N'-tetramethylethylenediamine)Ni(CH3COCHCOCH3)2 以 not given 为溶剂， 以61%的产率得到(TMEDA)Ni(CD3)2
  参考文献：
  名称：

  烷基-烷基交叉偶联催化剂的合成、电子结构和反应性中的配体氧化还原效应

  摘要：

  三联吡啶配体稳定镍烷基配合物的能力对于从根本上了解烷基-烷基交叉偶联反应中涉及的关键过程至关重要。在这里，使用同位素标记的 (TMEDA)NiMe(2)（TMEDA = N,N,N',N'-四甲基乙二胺）的机理研究表明，烷基 - 烷基交叉偶联反应中的一种重要催化剂（tpy'）NiMe（ 2b, tpy' = 4,4',4''-三叔丁基三联吡啶)，不是通过涉及形成甲基自由基的机制产生的。相反，有人提出在将三联吡啶配体添加到 (TMEDA)NiMe(2) 后，通过 Ni(II)-二甲基物种和溶液中的 Ni(0) 片段之间的比例反应产生（三联吡啶）NiMe 复合物。顺磁性（三联吡啶）NiMe (2a) 的 EPR 和 DFT 研究均表明未配对电子主要位于三联吡啶配体上，并且该镍配合物的正确电子描述是与还原的三联吡啶结合的 Ni(II)-甲基阳离子配体。因此，这些结果的一个重要结果是通过（三联吡啶

  DOI：

  10.1021/ja063334i

文献信息

• Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂
  作者：Ingrid Bach、Richard Goddard、Carsten Kopiske、Klaus Seevogel、Klaus-Richard Pörschke

  DOI：10.1021/om980705y

  日期：1999.1.1

  Oxidative addition of CH3I to (d(t)bpe)Ni(C2H4) (d(t)bpe = (Bu2PC2H4PBu2)-Bu-t-Bu-t) affords (d(t)bpe)-Ni(I)CH3 (I). The reaction of (d(t)bpe)NiCl2 or 1 with the stoichiometric quantity of (tmeda)Mg(CH3), yields (d(t)bpe)Ni(CH3)(2) (2). (d(t)bpe)Ni(I)CD3 (1-d(3)) and (d(t)bpe)Ni(CD3)(2) (2-d(6)) have been prepared analogously. Thermolysis of 2 in benzene affords (d(t)bpe)Ni}(2)(mu-eta(2):eta(2)-C6H6) (4). The reaction of either 2 or 4 with hydrogen (H-2, HD, D-2) gives (d(t)bpe)Ni}(2)(mu-H)(2) (3) and the isotopomers (d(t)bpe)Ni}(2)(mu-H)(mu-D) (3-d) and (d(t)bpe)Ni}(2)(mu-D)(2) (3-d(2)). According to the NMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3 have been determined by X-ray crystallography, Solution thermolysis of 2 or reduction of (dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves a-complex-type intermediates [(d(t)bpe)Ni(eta(2)-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(d(t)bpe)Ni-0] a-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy to handle starting complexes for [(d(t)bpe)Ni-0] reactions. Partial protolysis of 2 with CF3SO3H affords (d(t)bpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to give equimolar amounts of [(d(t)bpe)Ni(C2H5)](+)(OSO2CF3-) (6) and propene. The reaction is thought to be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate [(d(t)bpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydride intermediate [(d(t)bpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bond affords 6.