[(dtbpe)Ni(CH2CMe3)]PF6 | 765927-81-9

• 英文名称: [(dtbpe)Ni(CH2CMe3)]PF6
• 英文别名: [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CMe3)]PF6；[Ni(1,2-bis(di-tert-butylphosphino)ethane)(CH2-t-Bu)]PF6
• CAS: 765927-81-9
• 化学式: C₂₃H₅₁NiP₂*F₆P
• 分子量: 593.26
• InChiKey: UTSYUIVCONSNFH-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：

  [(dtbpe)Ni(CH2CMe3)]PF6 在 NaN(TMS)2 作用下， 以 not given 为溶剂， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CMe2CH2)]
  参考文献：
  名称：

  Preparation of Stable Alkyl Complexes of Ni(I) and Their One-Electron Oxidation to Ni(II) Complex Cations

  摘要：

  The three-coordinate nickel(I) alkyl complexes (dtbpe)Ni(CH2CMe3) (2), (dtbpe)Ni(CH2SiMe3) (3), and (dtbpe)Ni(CH2CMe2Ph) (4) have been prepared by treatment of [(dtbpe)NiCl]2 with alkyllithium reagents. While thermally robust, they each undergo mild one-electron oxidation to give the corresponding Ni(II) complex cations [(dtbpe)Ni(CH2CMe3)+] (5), [(dtbpe)Ni(CH2SiMe3)+] (6), and [(dtbpe)Ni(CH2CMe2Ph)+] (7) as red-brown [PF6-] or [BArF4-] salts. In contrast to cationic amido and phosphido analogues that undergo alpha-deprotonation to afford imido and phosphinidene derivatives, deprotonation of 5-7 occurs at a gamma-CH3 group to give metallacyclobutane products (dtbpe)Ni(CH2CMe2CH2) (8), (dtbpe)Ni(CH2SiMe2CH2) (9), and (dtbpe)Ni(CH2CPhMeCH2) (10), not (dtbpe)Ni=CHR.

  DOI：

  10.1021/ja047052z
• 作为产物：
  描述：

  ferrocenium hexafluorophosphate 、 (1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CMe3) 以 四氢呋喃 为溶剂， 生成 [(dtbpe)Ni(CH2CMe3)]PF6
  参考文献：
  名称：

  Preparation of Stable Alkyl Complexes of Ni(I) and Their One-Electron Oxidation to Ni(II) Complex Cations

  摘要：

  The three-coordinate nickel(I) alkyl complexes (dtbpe)Ni(CH2CMe3) (2), (dtbpe)Ni(CH2SiMe3) (3), and (dtbpe)Ni(CH2CMe2Ph) (4) have been prepared by treatment of [(dtbpe)NiCl]2 with alkyllithium reagents. While thermally robust, they each undergo mild one-electron oxidation to give the corresponding Ni(II) complex cations [(dtbpe)Ni(CH2CMe3)+] (5), [(dtbpe)Ni(CH2SiMe3)+] (6), and [(dtbpe)Ni(CH2CMe2Ph)+] (7) as red-brown [PF6-] or [BArF4-] salts. In contrast to cationic amido and phosphido analogues that undergo alpha-deprotonation to afford imido and phosphinidene derivatives, deprotonation of 5-7 occurs at a gamma-CH3 group to give metallacyclobutane products (dtbpe)Ni(CH2CMe2CH2) (8), (dtbpe)Ni(CH2SiMe2CH2) (9), and (dtbpe)Ni(CH2CPhMeCH2) (10), not (dtbpe)Ni=CHR.

  DOI：

  10.1021/ja047052z

文献信息

• Sequential Insertion Reactions of Carbon Monoxide and Ethylene into the Ni−C Bond of a Cationic Nickel(II) Alkyl Complex
  作者：John J. Curley、Kristina D. Kitiachvili、Rory Waterman、Gregory L. Hillhouse

  DOI：10.1021/om900023y

  日期：2009.4.27

  (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) sequentially inserts carbon monoxide and ethylene into the Ni−C bond to form isolable products. Upon exposure to carbon monoxide, 1 inserts 1 equiv of CO to give [(dtbpe)Ni(η2-C(O)CH2tBu)][PF6] (2). This cationic acyl complex reacts productively with ethylene, resulting in [(dtbpe)Ni(κ2-CH2CH2C(O)CH2tBu)][PF6] (3), in which the oxygen atom is bound

  阳离子镍（II）新戊基络合物[（dtbpe）Ni（CH 2 t Bu）] [PF 6 ]（1 ; dtbpe = 1,2-双（二叔丁基膦基）乙烷）依次将一氧化碳和乙烯插入Ni-C键形成可分离的产物。当暴露于一氧化碳，1个插入1个当量的CO，得到[（dtbpe）的Ni（η 2 -C（O）CH 2吨丁基）] [PF 6 ]（2）。此阳离子酰基复杂发生反应高效地与乙烯，得到[（dtbpe）的Ni（κ 2 -CH 2 CH 2 C（O）CH 2吨丁基）] [PF 6 ]（3），其中氧原子与Ni结合，形成五元金属环。的治疗2与苯基锂导致去质子化在邻近羰基的酸性亚甲基位置，得到中性烯酮络合物（dtbpe）的Ni（η 2 -OC═CH吨卜）（4）。复合物2，3和4是在20℃下稳定，并已通过NMR和IR光谱以及单晶X射线衍射。