(bis(diisopropylphosphino)ethane)Ni(CO)2 | 170656-93-6

• 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: (bis(diisopropylphosphino)ethane)Ni(CO)2
• 英文别名: [Ni(1,2-bis(di-isopropylphosphino)ethane)(CO)₂]；[(1,2-bis(diisopropylphosphino)ethane)Ni(μ-H)]2；[Ni(dippe)(CO)₂]；[(1,2-bis(diisopropylphosphino)ethane)Ni(CO)2]；[Ni(CO)2(1,2-bis(diisopropylphosphino)ethane)]；Ni(((i)Pr)2PCH2CH2P((i)Pr)2)(CO)2；Carbon monoxide;2-di(propan-2-yl)phosphanylethyl-di(propan-2-yl)phosphane;nickel
• CAS: 170656-93-6
• 化学式: C₁₆H₃₂NiO₂P₂
• 分子量: 377.066
• InChiKey: CCKYNEJNDMSHDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (bis(diisopropylphosphino)ethane)Ni(CO)2 、 联苯烯 生成 (bis(diisopropylphosphino)ethane)Ni(COC6H4C6H4)
  参考文献：
  名称：

  镍配合物催化碳-碳键的活化和功能化

  摘要：

  镍炔化合物（dippe）Ni（PhC⋮CPh），1，（dippe）Ni（MeC⋮CMe），2，（dippe）Ni（MeO 2 CC⋮CCO 2 Me），3，（dippe）Ni（CH合成了3 OCH 2 C⋮CCH 2 OCH 3）4和（dippe）Ni（CF 3 C⋮CCF 3）5（dippe =双（二异丙基膦基）乙烷），并用1 H，31 P和1 H表征。13 C { 1 H} NMR光谱。配合物1，2，和3用X射线晶体学表征。在过量的联苯和过量的炔烃存在下，配合物1或2（120°C）的热解反应会非常缓慢地催化形成相应的9,10-二取代的菲。但是，向反应混合物中添加约6 mol％O 2（基于金属络合物）会导致在较低温度（约70-80°C）下催化作用加快。配合物3或4与过量的联苯和过量的炔烃的热解导致炔烃环三聚产物作为反应中形成的主要有机物。通过加热（浸渍）Ni（CO）2催化生产芴酮也可以通过加热（浸渍）Ni（2

  DOI：

  10.1021/om990387i
• 作为产物：
  描述：

  [nickel(1,2-bis-(di-isopropylphosphino)ethane)(Me)2] 以 四氢呋喃 为溶剂， 生成 (bis(diisopropylphosphino)ethane)Ni(CO)2
  参考文献：
  名称：

  锂试剂替代氟化物。一种改进的羟基镍，铝和酰胺配合物的合成方法

  摘要：

  Ni（Me）（F）（dippe）络合物与Li（OH），Li（O t Bu）和Li（NC 4 H 8）进行干净的氟化物置换反应，提供相应的顺式羟基，烷氧基和氨基甲基衍生品。这些化合物显示出有限的热稳定性，并且在温和的条件下会因β-氢消除或歧化过程而分解。

  DOI：

  10.1021/om0489709

文献信息

• Acid−Base Reactions of Methylnickel Hydroxo, Alkoxo, and Amide Complexes with Carbon Acids. Studies on the Reactivity of Noncyclic Nickel Enolates
  作者：Juan Cámpora、Inmaculada Matas、Pilar Palma、Eleuterio Álvarez、Claudia Graiff、Antonio Tiripicchio

  DOI：10.1021/om7007259

  日期：2007.11.1

  complexes of composition Ni(Me)(X)(dippe) (X = OH, t-BuO, cyclo-NC4H8; dippe = i-Pr2PCH2CH2Pi-Pr2) react with enolizable ketones, esters, and nitriles, producing the corresponding enolate complexes. In the case of the hydroxo and alkoxo complexes, these reactions may lead to equilibrium mixtures, allowing a comparison of their respective basicities, while the amido compound reacts clean and quantitatively

  基本有机镍羟，组合物的Ni（ME）（X）（dippe）（X = OH，烷氧的，或酰氨基络合物吨-BuO，环-NC 4 H ^ 8 ; dippe =我-Pr 2 PCH 2 CH 2 P我- Pr 2）与可烯醇化的酮，酯和腈反应，生成相应的烯醇化物配合物。在羟基和烷氧基络合物的情况下，这些反应可导致平衡的混合物，从而可以比较它们各自的碱度，而酰胺基化合物在所有情况下均可以进行清洁且定量的反应，从而可以分离出相应的烯醇化物。酮衍生物显示出与氧结合的烯酸酯配体，而酯和腈烯酸酯则通过碳原子结合金属中心。苯乙酮烯醇盐配合物具有很强的亲核性质，可与醛（PhCHO）或CO 2迅速反应，提供相应的醛酸酯和羧酸酯加成产物。
• Addition reactions of O-bound cyclic nickel enolates to α,β-unsaturated ketones
  作者：Juan Cámpora、Celia M. Maya、Pilar Palma、Ernesto Carmona、Claudia Graiff、Antonio Tiripicchio

  DOI：10.1039/b303062h

  日期：——

  The addition of the O-bound nickel enolates Ni(C6H4-o-C(CHR)O)(dippe) (R = H, 1; R = Me, 2) to α,β-unsaturated ketones proceeds with complete stereoselectivity giving rise to [2 + 4] cycloadducts that can further evolve to generate open-chain, Michael-like products. The stereoselectivity of these reactions suggests a concerted mechanism, through an exo transition state.

  将 O 结合的镍烯醇化物 Ni(C6H4-oC(CHR)O)(dippe) (R = H, 1; R = Me, 2) 加入到 α,β-不饱和酮中以完全立体选择性进行，从而产生 [ 2 + 4] 环加合物，可以进一步进化产生开链的迈克尔样产物。这些反应的立体选择性通过外过渡态表明了一种协调的机制。
• Reduction of CO2 and SO2 with low valent nickel compounds under mild conditions
  作者：Lucero González-Sebastián、Marcos Flores-Alamo、Juventino J. García

  DOI：10.1039/c1dt10972c

  日期：——

  The reaction of [(dippe)Ni(μ-H)]2 (A) (dippe = 1,2-bis(diisopropyl-phosphinoethane) with CO2 in toluene afforded the carbonyl nickel(0) compounds of the type (dippe)Ni(CO)]2(μ-dippe)}(1) and (dippe)Ni(CO)(dippeO)] (2), which were characterized by standard spectroscopic methods; complex (1) was also characterized by single crystal X-ray diffraction. Reaction of (A) with SO2 yields the thiosulfate nickel(II) compound [Ni(dippe)(S2O3)] (5), which was fully characterized by standard spectroscopic methods and X-ray crystallography. In both cases, a reduction reaction of CO2 to CO and SO2 to S2O32− with (A) took place under mild conditions.

  在甲苯中，[(dippe)Ni(μ-H)]2 (A) (dippe = 1,2-双(二异丙基膦乙烷)与 CO2 反应，得到(dippe)Ni(CO)]2(μ-dippe)}(1) 和 (dippe)Ni(CO)(dippeO)] (2)类型的羰基镍(0)化合物，这些化合物用标准光谱方法进行了表征；复合物 (1) 还用单晶 X 射线衍射法进行了表征。(A)与二氧化硫反应生成硫代硫酸镍（II）化合物[Ni(dippe)(S2O3)](5)，并通过标准光谱方法和 X 射线晶体学对其进行了全面表征。在这两种情况下，CO2 与 (A) 发生还原反应生成 CO，SO2 与 (A) 发生还原反应生成 S2O32-。
• Nickel-Catalyzed Hydrosilylation of CO₂ in the Presence of Et₃B for the Synthesis of Formic Acid and Related Formates
  作者：Lucero González-Sebastián、Marcos Flores-Alamo、Juventino J. Garcı́a

  DOI：10.1021/om400876j

  日期：2013.12.9

  The reaction of CO2 with Et3SiH catalyzed by the nickel complex [(dippe)Ni(μ-H)]2 (1) afforded the reduction products Et3SiOCH2OSiEt3 (12%), Et3SiOCH3 (3%), and CO, which were characterized by standard spectroscopic methods. Part of the generated CO was found as the complex [(dippe)Ni(CO)]2 (2), which was characterized by single-crystal X-ray diffraction. When the same reaction was carried out in the

  CO的反应2用Et 3 SiH基催化的镍络合物[（dippe）的Ni（μ-H）] 2（1）得到的还原产物的Et 3的SiOCH 2 OSiEt 3（12％），等3的SiOCH 3（3 ％）和CO，用标准光谱法进行表征。发现一部分产生的CO为络合物[（dippe）Ni（CO）] 2（2），其特征在于单晶X射线衍射。当在路易斯酸（例如Et 3 B）的存在下进行相同的反应时，CO 2的氢化硅烷化有效地进行了甲硅烷基甲酸酯（Et 3 SiOC（O）H）的高收率（85-89％），在80°C下进行了1 h。还研究了甲硅烷基甲酸酯产生甲酸，甲酰胺和烷基甲酸酯的进一步反应性。
• Nickel-Catalyzed Reductive Hydroesterification of Styrenes Using CO₂ and MeOH
  作者：Lucero González-Sebastián、Marcos Flores-Alamo、Juventino J. García

  DOI：10.1021/om300819d

  日期：2012.12.10

  Complexes [(dippe)Ni(mu-H)](2) (A) (dippe = 1,2-bis-di-isopropylphosphino)ethane) and [(dtbpe)Ni(mu-H)](2) (B) (dtbpe = 1,2-bis-di-tert-butylphospino)ethane) catalyze the reductive hydroesterification of styrenes with the use of CO2 and MeOH. The latter acts as a hydrogen source and as an esterificating agent, to yield the corresponding branched and linear esters in moderate to good yields. In all of the studied reactions the linear esters were obtained in higher amounts than the branched ones. When the hydroesterification reaction was carried out using a stoichiometric metal/substrate ratio, the complexes [(P-P)Ni(CO)(2)] and [(P-P)Ni(CO3)] (P-P = dippe or dtbpe) were isolated and characterized by standard spectroscopic methods. Compounds [(dtbpe)Ni(CO)(2)] and [(dtbpe)Ni(CO3)] were also fully characterized by single-crystal X-ray diffraction.