[(1,2-bis(diisopropylphosphino)ethane)Ni(CN)₂] | 745020-45-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: [(1,2-bis(diisopropylphosphino)ethane)Ni(CN)₂]
• 英文别名: [(dippe)Ni(CN)₂]；[(1,2-bis(diisopropylphosphino)ethane)Ni(CN)2]；(1,2-bis(diisopropylphosphino)ethane)Ni(CN)2；[(dippe)Ni(CN)2]
• CAS: 745020-45-5
• 化学式: C₁₆H₃₂N₂NiP₂
• 分子量: 373.081
• InChiKey: RGHGYSIYHVGGNG-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

• 作为产物：
  描述：

  ((1,2-bis(diisopropylphosphino)ethane)NiH)2 以 氘代四氢呋喃 为溶剂， 反应 144.0h， 生成 [(1,2-bis(diisopropylphosphino)ethane)Ni(CN)₂]
  参考文献：
  名称：

  含镍的2-和3-呋喃腈中的 碳-碳vs.碳-氧键活化†

  摘要：

  [（dippe）NiH] 2（1）（dippe ＝ 1，2-双（二异丙基膦基）-乙烷）与2-和3-呋喃腈（2-FN和3-FN）之间的反应在室温下进行。既furonitriles最初用H反应2损失和协调一个[镍（dippe）]片段腈取代基以η 2 -C Ñ方式，得到配合物[（dippe）的Ni（η 2 -C，N- 2-FN） ]（2）和[（dippe）的Ni（η 2 -C，N- 3-FN）]（10）， 分别。稍微过量的每个腈的存在下，在室温下监测6天此反应后，C-CN键活化产物[（dippe）的Ni（CN）（η 1 -C- 2-FN）]（7）和[（dippe）的Ni（CN）（η 1 -C- 3-FN）]（11）观察为主要产品。这些配合物通过1 H，31 P { 1 H}和13 C { 1 H} NMR以及单晶X射线测定得到充分表征。分离并表征了（7）和（11），进行了热稳定性研究，结果发现两

  DOI：

  10.1039/c6ra20244f

文献信息

• Kinetics, Thermodynamics, and Effect of BPh₃ on Competitive C−C and C−H Bond Activation Reactions in the Interconversion of Allyl Cyanide by [Ni(dippe)]
  作者：Nicole M. Brunkan、Donna M. Brestensky、William D. Jones

  DOI：10.1021/ja037002e

  日期：2004.3.1

  longer reaction times, indicating that C-CN cleavage is reversible and the crotononitrile complexes 2 are more thermodynamically stable than eta(3)-allyl species 3. The kinetics of this reaction have been followed as a function of temperature, and rate constants have been extracted by modeling of the reaction. The rate constants for C-CN bond formation (the reverse of C-CN cleavage) show a stronger temperature

  [(dippe)Ni(micro-H)](2) 与烯丙基氰在低温下定量反应生成 eta(2)-烯烃配合物 (dippe)Ni(CH(2)=CHCH(2)CN) (1 ）。在室温或更高温度下，烯烃络合物转化为 C-CN 裂解产物 (dippe)Ni(eta(3)-allyl)(CN) (3) 和烯烃异构化产物 (dippe)Ni(eta) 的混合物(2)-巴豆腈）（顺式和反式 2），通过 CH 活化形成。后者是较长反应时间的唯一产物，表明 C-CN 裂解是可逆的，巴豆腈配合物 2 比 eta(3)-烯丙基物种 3 在热力学上更稳定。温度和速率常数已通过反应模型提取出来。C-CN 键形成的速率常数（C-CN 裂解的反向）显示出比 C-CN 和 CH 活化更强的温度依赖性，使得观察到的 CH 与 C-CN 裂解产物的分布强烈依赖于温度。C-CN 形成步骤的激活参数也与 C-CN 和 CH 裂解步骤（较大的
• Cleavage of Carbon−Carbon Bonds in Alkyl Cyanides Using Nickel(0)
  作者：Juventino J. García、Alma Arévalo、Nicole M. Brunkan、William D. Jones

  DOI：10.1021/om049700t

  日期：2004.8.1

  The reaction of the complex [(dippe)NiH](2) (1) with a variety of alkyl cyanides afforded nickel(0) compounds of the type [(dippe)Ni(eta(2)-RCN)], where R, = Me, Et, Pr, Pr-i, Bu-t, cyclopropyl, cyclobutyl, adamantyl (2-9, respectively). When compounds 2-9 were warmed to yield oxidative addition products, the thermal reaction proceeded only in the case of 2 to produce [(dippe)Ni(Me)(CN)](10). Photochemical activation did produce oxidative addition products from compounds 2-8, which rapidly evolved to the beta-elimination products of the organic moiety in most cases and to the formation of [(dippe)Ni(CN)(2)] (11). Reaction of 1 with acetonitrile in the presence of BPh3 gives [(dippe)Ni(eta(2)-MeCNBPh3)](12), which does not undergo thermal C-CN cleavage upon heating. X-ray crystal structures are reported for 10-12.
• Competitive Carbon−Sulfur vs Carbon−Carbon Bond Activation of 2-Cyanothiophene with [Ni(dippe)H]₂
  作者：Matthew R. Grochowski、Ting Li、William W. Brennessel、William D. Jones

  DOI：10.1021/ja104158h

  日期：2010.9.8

  The processes of C C and C S bond cleavage have been studied with the homogeneous organometallic compound [Ni(dippe)H](2) (1). When 1 is reacted with 2-cyanothiophene at room temperature, cleavage of the nitrile-substituted C S bond occurs, forming the Ni-metallacycle complex (dippe)Ni(kappa(2)-S,C-SCH=CHCH=C(CN)) (2a), which has been fully characterized by NMR spectroscopy and X-ray diffraction. 2a was converted to the C CN cleavage product (dippe)Ni(CN)(2-thiophenyl) (3) when heated in solution. On closer inspection, four other intermediates were observed by P-31 NMR spectroscopy at low temperature. Structures for the intermediates were elucidated through a combination of independent synthesis, theoretical calculations, chemical characterization, and experimental precedent. A kinetic product (dippe)Ni(kappa(2)-S,C-SC(CN)=CHCH=CH) (2b) was formed from cleavage of the nonsubstituted C S bond, as well as a Ni(0) eta(2)-nitrile intermediate, (dippe)Ni(eta(2)-C,N-2-cyanothiophene) (4), and a dinuclear mixed Ni(0) Ni(II) product (6b). A complete DFT analysis of this system has been carried out to reveal comparative details about the two bond cleavage transition states.