tert-butylazanide;nickel(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene | 174355-57-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: tert-butylazanide;nickel(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 174355-57-8
• 化学式: C₂₈H₅₀N₂Ni₂
• 分子量: 532.098
• InChiKey: SIBVCHWNVFTLQQ-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：

  tert-butylazanide;nickel(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene 在 CO 作用下， 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, Characterization, Isomerization, and Reactivity of Dimeric Cyclopentadienylnickel Amido Complexes

  摘要：

  The first cyclopentadienylnickel amido complexes have been isolated and characterized as [(eta-C(5)Me(4)R')Ni(mu-NHR)](2) (R = Ph, p-tol, 2,6-xyl, (t)Bu; R' = Me, Et). These complexes are dimers in solution and in the solid state, as shown by the synthesis of mixed amido complexes, by NMR spectroscopy, and by crystallographic studies on cis-[Cp(Et)Ni(mu-NH(p-tol))](2) (cis-1'), trans-[Cp(Et)Ni(mu-NH(2,6-xylyl))](2) (trans-3'), and cis-[Cp(Et)Ni(mu-NH(t)Bu)](2) (4') (Cp(Et) = eta-C(5)Me(4)Et). Resonances in the H-1 NMR spectra of these diamagnetic dimers display unusual chemical shifts that are explained on the basis of ring-current anisotropy and inductive effects. The dimers undergo reversible cis/trans isomerization at elevated temperatures; mechanistic studies indicate that this process proceeds through cleavage of one dative nitrogen-nickel bond, rate-limiting rotation of the amido group, and recoordination to regenerate the bridge. Dimethylzirconocene was essential as a scavenger for trace water in these studies. The dimer [Cp*Ni(mu-NH(p-tol))](2) (1) reacts with CO and with (t)BuNC to give the insertion products Cp*Ni(CO)(C(O)NH(p-tol)) (6) and Cp*Ni(CN(t)Bu)(C(N(t)Bu)NH(p-tol)) (7), respectively, and with PMe(3) to give the unstable monomeric amido complex Cp*Ni(PMe(3))(NH(p-tol)) (5).

  DOI：

  10.1021/ja952882l
• 作为产物：
  描述：

  (acetylacetonato)(η5-pentamethylcycopentadienyl)nickel(II) 、 lithium tert-butylamide 以 四氢呋喃 为溶剂， 以66.7%的产率得到tert-butylazanide;nickel(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene
  参考文献：
  名称：

  Synthesis, Characterization, Isomerization, and Reactivity of Dimeric Cyclopentadienylnickel Amido Complexes

  摘要：

  The first cyclopentadienylnickel amido complexes have been isolated and characterized as [(eta-C(5)Me(4)R')Ni(mu-NHR)](2) (R = Ph, p-tol, 2,6-xyl, (t)Bu; R' = Me, Et). These complexes are dimers in solution and in the solid state, as shown by the synthesis of mixed amido complexes, by NMR spectroscopy, and by crystallographic studies on cis-[Cp(Et)Ni(mu-NH(p-tol))](2) (cis-1'), trans-[Cp(Et)Ni(mu-NH(2,6-xylyl))](2) (trans-3'), and cis-[Cp(Et)Ni(mu-NH(t)Bu)](2) (4') (Cp(Et) = eta-C(5)Me(4)Et). Resonances in the H-1 NMR spectra of these diamagnetic dimers display unusual chemical shifts that are explained on the basis of ring-current anisotropy and inductive effects. The dimers undergo reversible cis/trans isomerization at elevated temperatures; mechanistic studies indicate that this process proceeds through cleavage of one dative nitrogen-nickel bond, rate-limiting rotation of the amido group, and recoordination to regenerate the bridge. Dimethylzirconocene was essential as a scavenger for trace water in these studies. The dimer [Cp*Ni(mu-NH(p-tol))](2) (1) reacts with CO and with (t)BuNC to give the insertion products Cp*Ni(CO)(C(O)NH(p-tol)) (6) and Cp*Ni(CN(t)Bu)(C(N(t)Bu)NH(p-tol)) (7), respectively, and with PMe(3) to give the unstable monomeric amido complex Cp*Ni(PMe(3))(NH(p-tol)) (5).

  DOI：

  10.1021/ja952882l