(C5H5)2YbPzMe2(THF) | 639512-42-8

• 英文名称: (C5H5)2YbPzMe2(THF)
• CAS: 639512-42-8
• 化学式: C₁₉H₂₅N₂OYb
• 分子量: 470.46
• InChiKey: YHJFVWHCHZJISJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (C5H5)2YbPzMe2(THF) 、 异氰酸苯酯 以 四氢呋喃 为溶剂， 以64%的产率得到(C5H5)2Yb[OC(3,5-dimethylpyrazole)=NPh](THF)
  参考文献：
  名称：

  Synthesis and Studies on the Reactivities of Dicyclopentadienylytterbium Derivatives Containing Carbazolate and Pyrazolate Ligands

  摘要：

  Two ytterbocene derivatives containing aromatic nitrogen ligands, (C5H5)(2)YbCbz(THF) (1) and (C5H5)(2)YbPzMe(2)(THF) (4), were synthesized, and their reactivities toward N,N'-diisopropylcarbodiimide, phenyl isothiocyanate, and phenyl isocyanate were studied. Abstraction of cyclopentadienyl from (C5H5)(3)Yb with 1 equiv of carbazole (HCbz) in THF at room temperature gives 1. Reaction of 1 with N,N'-diisopropylcarbodiimide ((PrN)-Pr-i=C=(NPr)-Pr-i) results in monoinsertion of (PrN)-Pr-i=C=(NPr)-Pr-i into the Yb-N(Carbazolate) bond, yielding the ytterbocene guanidinate (C5H5)(2)Yb[(PrN)-Pr-i - C(Cbz) - (NPr)-Pr-i] (2), while treatment of 1 with 1 equiv of phenyl isothiocyanate (PhNCS) gives the unexpected monocyclopentadienylytterbium complex (C5H5)Yb[S - C(Cbz) - NPh](2)(THF) (3) and (C5H5)(3)Yb(THF), which may be rationalized by the ligand rearrangement of the monoinsertion product (C5H5)(2)Yb[S - C(Cbz) - NPh]. (C5H5)(3)Yb reacts with 3,5-dimethylpyrazole (HPzMe(2)) in a 1:1 ratio at ambient temperature to form complex 4. Reaction of 4 with PhNCO gives the insertion product (C5H5)(2)Yb[OC(=NPh)-PzMe(2)](THF) (5). In contrast to 1, however, complex 4 does not react with (PrNCNPr)-Pr-i-Pr-i under the same conditions. All these complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 2-5 were also determined by X-ray single-crystal diffraction analyses. These reactions present the first example of 1,3-heterocumulene insertions into the Ln-N(aromatic ring) bond and provide a new strategy for introducing a substituent at the nitrogen atom of organic heterocycle compounds.

  DOI：

  10.1021/om0340342
• 作为产物：
  描述：

  四氢呋喃 、 3,5-二甲基吡唑 、 tris(cyclopentadienyl)ytterbium(III) 以 四氢呋喃 为溶剂， 以72%的产率得到(C5H5)2YbPzMe2(THF)
  参考文献：
  名称：

  Synthesis and Studies on the Reactivities of Dicyclopentadienylytterbium Derivatives Containing Carbazolate and Pyrazolate Ligands

  摘要：

  Two ytterbocene derivatives containing aromatic nitrogen ligands, (C5H5)(2)YbCbz(THF) (1) and (C5H5)(2)YbPzMe(2)(THF) (4), were synthesized, and their reactivities toward N,N'-diisopropylcarbodiimide, phenyl isothiocyanate, and phenyl isocyanate were studied. Abstraction of cyclopentadienyl from (C5H5)(3)Yb with 1 equiv of carbazole (HCbz) in THF at room temperature gives 1. Reaction of 1 with N,N'-diisopropylcarbodiimide ((PrN)-Pr-i=C=(NPr)-Pr-i) results in monoinsertion of (PrN)-Pr-i=C=(NPr)-Pr-i into the Yb-N(Carbazolate) bond, yielding the ytterbocene guanidinate (C5H5)(2)Yb[(PrN)-Pr-i - C(Cbz) - (NPr)-Pr-i] (2), while treatment of 1 with 1 equiv of phenyl isothiocyanate (PhNCS) gives the unexpected monocyclopentadienylytterbium complex (C5H5)Yb[S - C(Cbz) - NPh](2)(THF) (3) and (C5H5)(3)Yb(THF), which may be rationalized by the ligand rearrangement of the monoinsertion product (C5H5)(2)Yb[S - C(Cbz) - NPh]. (C5H5)(3)Yb reacts with 3,5-dimethylpyrazole (HPzMe(2)) in a 1:1 ratio at ambient temperature to form complex 4. Reaction of 4 with PhNCO gives the insertion product (C5H5)(2)Yb[OC(=NPh)-PzMe(2)](THF) (5). In contrast to 1, however, complex 4 does not react with (PrNCNPr)-Pr-i-Pr-i under the same conditions. All these complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 2-5 were also determined by X-ray single-crystal diffraction analyses. These reactions present the first example of 1,3-heterocumulene insertions into the Ln-N(aromatic ring) bond and provide a new strategy for introducing a substituent at the nitrogen atom of organic heterocycle compounds.

  DOI：

  10.1021/om0340342