Ni2(P(CH3)3)2(3,5-dimethylpyrazolate-κN)(.m.2-η1:η3-CH2-o-C6H4)(μ2-3,5-dimethylpyrazolate-κNN') | 285570-77-6

• 英文名称: Ni2(P(CH3)3)2(3,5-dimethylpyrazolate-κN)(.m.2-η1:η3-CH2-o-C6H4)(μ2-3,5-dimethylpyrazolate-κNN')
• CAS: 285570-77-6
• 化学式: C₂₃H₃₈N₄Ni₂P₂
• 分子量: 549.909
• InChiKey: YZXJWGCPUZSNQE-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：

  Ni2(P(CH3)3)2(3,5-di-tert-butylpyrazolate-κN)(μ2-η1:η3-CH2-o-C6H4)(μ2-3,5-di-tert-butylpyrazolate-κN,N') 、 Ni2(P(CH3)3)2(3,5-dimethylpyrazolate-κN)(.m.2-η1:η3-CH2-o-C6H4)(μ2-3,5-dimethylpyrazolate-κNN') 以 二氯甲烷-D2 为溶剂， 生成 Ni2(P(CH3)3)2(3,5-di-tert-butylpyrazolate-κN)(μ2-η1:η3-CH2-o-C6H4)(μ2-3,5-dimethylpyrazolate-κNN')
  参考文献：
  名称：

  Ligand Exchange on Pyrazolate-κN-μ-pyrazolate and Pyrazole-κN-μ-pyrazolate Binuclear Nickel Complexes

  摘要：

  Compounds containing bridging pyrazolate and terminal pyrazolate or pyrazole ligands of type Ni-2(PMe3)(2)(L-kappa N)(mu(2)-eta(1):eta(3)-CH2-o-C6H4)(mu(2)-L-kappa N,N') (L = 3,5-dimethylpyrazolate (Pz "), 3b, or 3,5-di-tert-butylpyrazolate (Pz**), 3c); Ni-2(PMe3)(2)(Pz**-kappa N)(mu(2-)eta(1);eta(3)-CH2-o-C6H4)(mu(2)-Pz "-kappa N,N') , 4, and [Ni-2(PMe3)(2)(HPz "-kappa N)(mu(2)-eta(1):eta(3)-CH2-o-C6H4)(mu(2)-Pz-kappa NN')](X) (X = Br, 5, or BPh4, 6) have been prepared. Spin saturation transfer experiments reveal a slow motion of the terminal pyrazolate ligand of 3b and 4, consisting of a combination of N,N-metallotropic shift and rotation around the Ni-N bond, but did not show any exchange of the bridging and terminal pyrazolate ligands. However, the mixed ligand derivative 4 can be obtained by conproportionation of 3b and Sc. This reaction reveals a slow intermolecular bridging-terminal as well as intermolecular pyrazolate exchange. In contrast with complexes of type 3 and 4, the formally cationic 5 and 6 display dynamic NMR spectra at room temperature due to their occurrence in solution as a mixture of rapidly exchanging isomers. Variable temperature NMR experiments have shown that 5 also undergoes a highly stereoselective HPz/Br- exchange.

  DOI：

  10.1021/om000044g
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 Ni2Br2(PMe3)3(μ2-η(3):η(1)-CH2-o-C6H4) 在 Tl(OC₂H₅) 作用下， 以 四氢呋喃 为溶剂， 以90-93的产率得到Ni2(P(CH3)3)2(3,5-dimethylpyrazolate-κN)(.m.2-η1:η3-CH2-o-C6H4)(μ2-3,5-dimethylpyrazolate-κNN')
  参考文献：
  名称：

  Ligand Exchange on Pyrazolate-κN-μ-pyrazolate and Pyrazole-κN-μ-pyrazolate Binuclear Nickel Complexes

  摘要：

  Compounds containing bridging pyrazolate and terminal pyrazolate or pyrazole ligands of type Ni-2(PMe3)(2)(L-kappa N)(mu(2)-eta(1):eta(3)-CH2-o-C6H4)(mu(2)-L-kappa N,N') (L = 3,5-dimethylpyrazolate (Pz "), 3b, or 3,5-di-tert-butylpyrazolate (Pz**), 3c); Ni-2(PMe3)(2)(Pz**-kappa N)(mu(2-)eta(1);eta(3)-CH2-o-C6H4)(mu(2)-Pz "-kappa N,N') , 4, and [Ni-2(PMe3)(2)(HPz "-kappa N)(mu(2)-eta(1):eta(3)-CH2-o-C6H4)(mu(2)-Pz-kappa NN')](X) (X = Br, 5, or BPh4, 6) have been prepared. Spin saturation transfer experiments reveal a slow motion of the terminal pyrazolate ligand of 3b and 4, consisting of a combination of N,N-metallotropic shift and rotation around the Ni-N bond, but did not show any exchange of the bridging and terminal pyrazolate ligands. However, the mixed ligand derivative 4 can be obtained by conproportionation of 3b and Sc. This reaction reveals a slow intermolecular bridging-terminal as well as intermolecular pyrazolate exchange. In contrast with complexes of type 3 and 4, the formally cationic 5 and 6 display dynamic NMR spectra at room temperature due to their occurrence in solution as a mixture of rapidly exchanging isomers. Variable temperature NMR experiments have shown that 5 also undergoes a highly stereoselective HPz/Br- exchange.

  DOI：

  10.1021/om000044g