ethene-bis(tricyclohexylphosphane)-nickel(0) | 41685-59-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: ethene-bis(tricyclohexylphosphane)-nickel(0)
• 英文别名: ethene;nickel;tricyclohexylphosphane
• CAS: 41685-59-0
• 化学式: C₃₈H₇₀NiP₂
• 分子量: 647.611
• InChiKey: WHSDAOPXSDERMO-UHFFFAOYSA-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：

  ethene-bis(tricyclohexylphosphane)-nickel(0) 在 二硫化碳 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Poppitz, W.; Uhlig, E., Zeitschrift fur Anorganische und Allgemeine Chemie

  摘要：

  DOI：
• 作为产物：
  描述：

  [Ni(PCy₃)₂]₂(N₂) 、 diethylmagnesium dioxane complex 以 四氢呋喃 为溶剂， 生成 ethene-bis(tricyclohexylphosphane)-nickel(0)
  参考文献：
  名称：

  Yamamoto, Akio; Miura, Yoshikiyo; Ito, Takashi, Organometallics, 1983, vol. 2, # 10, p. 1429 - 1436

  摘要：

  DOI：
• 作为试剂：
  描述：

  1,4-二(哌啶-1-基)-2-丁炔 在 ethene-bis(tricyclohexylphosphane)-nickel(0) 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以40%的产率得到Hexakis(N-piperidinomethyl)benzen
  参考文献：
  名称：

  Rosenthal, Uwe; Schulz, Wolfgang, Journal fur praktische Chemie (Leipzig 1954), 1986, vol. 328, # 3, p. 335 - 341

  摘要：

  DOI：

文献信息

• Synthesis and Reactions of Nickel(0) η²-Cyclohexyne Complexes and X-ray Crystal Structure of Ni(η²-C₆H₈)((C₆H₁₁)₂PCH₂CH₂P(C₆H₁₁)₂)
  作者：Martin A. Bennett、Julian A. Johnson、Anthony C. Willis

  DOI：10.1021/om9504516

  日期：1996.1.9

  sodium amalgam in the presence of Ni(η2-C2H4)L2 gives cyclohexyne nickel(0) complexes Ni(η2-C6H8)L2 [L2 = 2PPh3 (1), dcpe (2), 2PEt3 (3); dcpe = 1,2-bis(dicyclohexylphosphino)ethane, Cy2PCH2CH2PCy2], which are structurally similar to, but less stable than, the corresponding platinum(0) compounds. The crystal structure of 2 has been determined. The molecule contains a nickel atom bound to η2-cyclohexyne

  在Ni的存在1％钠汞齐1,2- dibromocyclohexene的减少（η 2 -C 2 H ^ 4）L- 2给出cyclohexyne镍（0）络合物的Ni（η 2 -C 6 H ^ 8）L- 2 [L 2 = 2PPh 3（1），dCPE（2），2PEt 3（3）; dCPE = 1,2-双（二环己基膦基）乙烷，Cy 2 PCH 2 CH 2 PCy 2 ]，其结构类似于相应的Platinum（0）化合物，但稳定性较差。的晶体结构2已确定。分子中含有结合到η镍原子2 -cyclohexyne [Ni基C（1）= 1.875（4），镍- C（2）= 1.867（4）]并DCPE [镀Ni-P（1）= 2.139（1）Å，Ni-P（2）= 2.138（1）Å]。几何形状是接近三角平面如果协调三键的中点被视为占据一个配位位置，而C的距离c [1.272（5）]比在铂（略少η 2 -C 6
• Mono- and bis(ethyne)nickel(0) complexes
  作者：Klaus Richard Poerschke

  DOI：10.1021/ja00197a029

  日期：1989.7

  Reactions de complexes du nickel avec l'acetylene pour aboutir a des complexes de types (R 3 P) 2 Ni(C 2 H 2 ), [(RO) 3 P] 2 , Ni(C 2 H 2 ), (t-BuNC) 2 Ni(C 2 H 2 ), [(R 3 P)Ni(C 2 H 2 )(C 2 H 4 )], [(R 3 P)Ni(C 2 H 4 ) 2 (μ-C 2 H 2 )] et (R 3 P)Ni(C 2 H 2 ) 2

  Reactions de complexes du Nickel avec l'乙炔浇注关于一种 des complexes de type (R 3 P) 2 Ni(C 2 H 2 ), [(RO) 3 P] 2 , Ni(C 2 H 2 ), (t- BuNC) 2 Ni(C 2 H 2 ), [(R 3 P)Ni(C 2 H 2 )(C 2 H 4 )], [(R 3 P)Ni(C 2 H 4 ) 2 (μ-C 2 H 2 )] et (R 3 P)Ni(C 2 H 2 ) 2
• Nickel-Catalyzed Formation of 1,3-Dienes via a Highly Selective Cross-Tetramerization of Tetrafluoroethylene, Styrenes, Alkynes, and Ethylene
  作者：Takuya Kawashima、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/jacs.7b12007

  日期：2017.12.13

  In the presence of a catalytic amount of Ni(cod)2 (cod = 1,5-cyclooctadiene) and PCy3 (Cy = cyclohexyl), the cross-tetramerization of tetrafluoroethylene (TFE), alkynes, and ethylene occurred in a highly selective manner to afford a variety of 1,3-dienes with a 3,3,4,4-tetrafluorobutyl chain. In addition, a Ni(0)-catalyzed cross-tetramerization of TFE, alkynes, ethylene, and styrenes was developed

  在催化量的 Ni(cod)2 (cod = 1,5-环辛二烯) 和 PCy3 (Cy = 环己基) 存在下，四氟乙烯 (TFE)、炔烃和乙烯的交叉四聚反应以高度选择性的方式发生得到各种具有 3,3,4,4-四氟丁基链的 1,3-二烯。此外，还开发了 Ni(0) 催化的 TFE、炔烃、乙烯和苯乙烯的交叉四聚反应。这些催化反应可能通过部分氟化的五元和七元镍环关键中间体进行。
• Binukleare organonickel(II)-verbindungen
  作者：B. Hipler、E. Uhlig、J. Vogel

  DOI：10.1016/s0022-328x(00)80994-8

  日期：1981.9

  of α,α′-dichloro-p-xylene to (PCY3)2Ni(C2H4)/ Ni(COD)2 affords the nickel(II) complex [(PCy3)NiCl]2(p-CH2C6H4CH2). By the reaction of α,α′-dibromo-o-xylene or α,α′-dibromo-2,3-dimethyl-naphthalene and (PCy3)2Ni(C2H4) or (PPh3)2Ni(C2H4 binuclear complexes but no metallacycles are obtained. With nickel(II) or nickel(I) halide complexes organodilithium compounds react either by partial substitution of

  将α，α'-二氯对二甲苯氧化成（PCY 3）2 Ni（C 2 H 4）/ Ni（COD）2可以得到镍（II）络合物[（PCy 3）NiCl] 2（p -CH 2 C 6 H 4 CH 2）。通过α，α'-二溴邻二甲苯或α，α'-二溴-2,3-二甲基萘与（PCy 3）2 Ni（C 2 H 4）或（PPh 3）2 Ni（ C 2高4双核配合物，但未获得金属环。有机二锂化合物与镍（II）或镍（I）卤化物络合物反应，可以通过从（PPh 3）2 NiBr 2和（PPh 3）2取代卤化物（形成[PPh 3）2 NiBr] 2（p -C 6 H 4）来进行反应。对-二硫代苯）或还原。一些新的紫色配合物是顺磁性的。
• Combined Experimental and Theoretical Study on the Reductive Cleavage of Inert C–O Bonds with Silanes: Ruling out a Classical Ni(0)/Ni(II) Catalytic Couple and Evidence for Ni(I) Intermediates
  作者：Josep Cornella、Enrique Gómez-Bengoa、Ruben Martin

  DOI：10.1021/ja311940s

  日期：2013.2.6

  A mechanistic and computational study on the reductive cleavage of C-OMe bonds catalyzed by Ni(COD)(2)/PCy3 with silanes as reducing agents is reported herein. Specifically, we demonstrate that the mechanism for this transformation does not proceed via oxidative addition of the Ni(0) precatalyst into the C-OMe bond. In the absence of an external reducing agent, the in-situ-generated oxidative addition complexes rapidly undergo beta-hydride elimination at room temperature, ultimately leading to either Ni(0)-carbonyl- or Ni(0)-aldehyde-bound complexes. Characterization of these complexes by X-ray crystallography unambiguously suggested a different mechanistic scenario when silanes are present in the reaction media. Isotopic-labeling experiments, kinetic isotope effects, and computational studies clearly reinforced this perception. Additionally, we also found that water has a deleterious effect by deactivating the Ni catalyst via formation of a new Ni-bridged hydroxo species that was characterized by X-ray crystallography. The order in each component was determined by plotting the initial rates of the C-OMe bond cleavage at varying concentrations. These data together with the in-situ-monitoring experiments by H-1 NMR, EPR, IR spectroscopy, and theoretical calculations provided a mechanistic picture that involves Ni(I) as the key reaction intermediates, which are generated via comproportionation of initially formed Ni(II) species. This study strongly supports that a classical Ni(0)/Ni(II) for C-OMe bond cleavage is not operating, thus opening up new perspectives to be implemented in other related C-O bond-cleavage reactions.