[(1,2-bis(di-tert-butylphosphino)ethane)NiI₂] | 220135-29-5

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: [(1,2-bis(di-tert-butylphosphino)ethane)NiI₂]
• 英文别名: [(dtbpe)NiI₂]；ditert-butyl(2-ditert-butylphosphanylethyl)phosphane;diiodonickel
• CAS: 220135-29-5
• 化学式: C₁₈H₄₀I₂NiP₂
• 分子量: 630.962
• InChiKey: HUAUHBUMRPJPRM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.15
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(1,2-bis(di-tert-butylphosphino)ethane)NiI₂] 、 [(1,2-bis(di-tert-butylphosphino)ethane)Ni(η2-methyl acrylate)] 以 二氯甲烷-D2 为溶剂， 反应 0.5h， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)NiI] 、 丙烯酸甲酯（MA）
  参考文献：
  名称：

  Mechanistic Details of the Nickel-Mediated Formation of Acrylates from CO₂, Ethylene and Methyl Iodide

  摘要：

  Methyl iodide induces the stoichiometric cleavage of nickelalactones, which are key intermediates in the nickel-mediated reaction of CO2 and alkenes to acrylates. Herein, we propose a modified and extended mechanism for this reaction on the basis of theoretical and experimental investigations for the bidentate P ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe). The calculated elementary steps agree well with experimental findings: reaction barriers are reasonable and explain the facile liberation of acrylate from a nickelalactone by methyl iodide. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Additionally, we have identified unproductive pathways leading to byproducts (e.g., propionates and catalytically inactive organometallic species). Although those side reactions can be suppressed to a certain extent, the strong binding of acrylate to nickel prevents a catalytic reaction, at least for the chosen ligand.

  DOI：

  10.1021/om400262b
• 作为产物：
  描述：

  以 四氢呋喃 为溶剂， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)NiI₂]
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂

  摘要：

  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.

  DOI：

  10.1021/om980705y

文献信息

• Synthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation
  作者：Addison N. Desnoyer、Eric G. Bowes、Brian O. Patrick、Jennifer A. Love

  DOI：10.1021/jacs.5b06735

  日期：2015.10.14

  frequently invoked as reactive intermediates in catalytic reactions of epoxides using nickel, but have never been isolated or experimentally observed in these transformations. Herein, we report the preparation of a series of well-defined nickelaoxetanes formed via the oxidative addition of nickel(0) with epoxides featuring ketones. The stereochemistry of the products is retained, which has not yet been reported

  2-镍氧杂环丁烷经常被用作使用镍的环氧化物催化反应中的反应中间体，但在这些转化中从未被分离或通过实验观察到。在此，我们报告了通过将镍 (0) 与具有酮的环氧化物氧化加成形成的一系列明确定义的镍氧杂环丁烷的制备。保留了产物的立体化学，尚未报道镍氧杂环丁烷。理论计算支持通过协同氧化加成的双金属开环/闭环途径。镍氧杂环丁烷的初始反应性研究表明，当用适当的试剂处理时，会发生质子分解、氧化诱导的还原消除、脱氧和消除反应。