[(1,2-bis(di-tert-butylphosphino)ethane)NiMeI] | 220135-19-3

• 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)NiMeI]
• 英文别名: [(dtbpe)NiMeI]
• CAS: 220135-19-3
• 化学式: C₁₉H₄₃INiP₂
• 分子量: 519.092
• InChiKey: IYHKSRCDYNJTEA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [(1,2-bis(di-tert-butylphosphino)ethane)NiMeI] 以 四氢呋喃 、 氘代苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 24.0h， 生成 [Ni(1,2-bis(di-tert-butylphosphino)ethane)(CO)2]
  参考文献：
  名称：

  使用低价镍络合物探索区域选择性键裂解和交叉偶联反应

  摘要：

  最近，酯作为交叉偶联反应的重金属化伙伴受到了广泛关注。在本文中，我们报道了一系列酯和硫酯的具有的反应性的系统研究[{（dtbpe）的Ni} 2（μ-η 2：η 2 -C 6 H ^ 6）]（dtbpe = 1,2-双（二（叔丁基）膦乙烷乙烷），它是（dtbpe）镍（0）的来源。发现Trifluoromethylthioesters以形成η 2 -羰基络合物。相比之下，乙酰硫酯经历了快速的C酰基反应-S键裂解，然后脱羰以生成甲基镍络合物。该脱羰基可以通过添加CO而向后推动，从而使硫酯再生。发现大多数硫酯配合物与苯基硼酸发生化学计量交叉偶联，生成硫化物。虽然三氟乙酸乙酯还发现，形成η 2 -羰基络合物，苯基酯被发现主要经历Ç芳-O键裂解产生芳基镍络合物。这些也可以进行金属转移以产生联芳基。配体争夺产生双（乙酸）镍配合物阻碍了使反应具有催化性的尝试，其形成受到独立合成的支持。最后，乙酸2-萘酯也

  DOI：

  10.1002/chem.201504959
• 作为产物：
  描述：

  ((CH₃)3C)2PC₂H₄P(C(CH₃)3)2Ni(CH₃)2 以 乙醚 为溶剂， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)NiMeI]
  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

• Mechanistic Details of the Nickel-Mediated Formation of Acrylates from CO₂, Ethylene and Methyl Iodide
  作者：Philipp N. Plessow、Laura Weigel、Ronald Lindner、Ansgar Schäfer、Frank Rominger、Michael Limbach、Peter Hofmann

  DOI：10.1021/om400262b

  日期：2013.6.10

  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.