[η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]dichloro(tetrahydrofuran)zirconium | 162053-50-1

• 英文名称: [η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]dichloro(tetrahydrofuran)zirconium
• CAS: 162053-50-1
• 化学式: C₂₃H₃₁Cl₂NOSiZr
• 分子量: 527.721
• InChiKey: RFIBSXVWGBFVNY-UHFFFAOYSA-L

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：
  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：

  [η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]dichloro(tetrahydrofuran)zirconium 、 苯基氯化镁 以 四氢呋喃 、 乙醚 为溶剂， 以40%的产率得到[η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]diphenylzirconium
  参考文献：
  名称：

  含连接的酰胺基-氟烯基配体的锆配合物的合成与表征

  摘要：

  Zirconium complexes containing an amido-fluorenyl ligand bridged by a dimethylsilylene group, C(13)H(8)SiMe(2)NCMe(3), have been synthesized. The dichloro complexes Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))Cl-2(L) (L = THF, Et(2)O) were prepared by reacting ZrCl(4)L(2) with Li-2[C13H8-SiMe(2)NCMe(3)] and characterized as labile mono(solvent) adducts. Reaction with MeMgCl gives the thermally sensitive dimethyl complex Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Me(2)(THF), whereas solvent-free dialkyl derivatives Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Ph(2) and Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))(CH(2)SiMe(3) )2, all under preservation of the chelate structure, are obtained with PhMgCl and Me(3)SiCH(2)MgCl, respectively. Variable-temperature H-1 NMR spectroscopic data reveal a sterically congested ligand sphere around the zirconium atom which is confirmed by a single-crystal X-ray diffraction study in the case of the bis(trimethylsilylmethyl) derivative. The substituted fluorenyl ligand is pentahapto-bonded with some variation of the zirconium-ring carbon bond lengths. The amido nitrogen is trigonal planar as a result of significant pi-donatian to the zirconium. The two (trimethylsilyl)methyl groups do not appear to be strongly distorted despite being bound to a 12-electron d(0) center but give rise to a conformation in which the repulsion between the trimethylsilyl and the tert-butyl groups is minimized. This compound crystallizes from pentane in the monoclinic space group P2(1)/n with a = 9.326(3), b = 16.806(5), and c = 19.638(6) Angstrom, beta = 93.23(2)degrees, V = 3073(2) Angstrom(3), Z = 4,R = 0.0308, wR(2) = 0.079.

  DOI：

  10.1021/om00002a028
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 [η1:η3-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl titanium 在 n-butyllithium 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 以56.1%的产率得到[η(1):η(5)-tert-butyl(dimethylfluorenylsilyl)amido]dichloro(tetrahydrofuran)zirconium
  参考文献：
  名称：

  含连接的酰胺基-氟烯基配体的锆配合物的合成与表征

  摘要：

  Zirconium complexes containing an amido-fluorenyl ligand bridged by a dimethylsilylene group, C(13)H(8)SiMe(2)NCMe(3), have been synthesized. The dichloro complexes Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))Cl-2(L) (L = THF, Et(2)O) were prepared by reacting ZrCl(4)L(2) with Li-2[C13H8-SiMe(2)NCMe(3)] and characterized as labile mono(solvent) adducts. Reaction with MeMgCl gives the thermally sensitive dimethyl complex Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Me(2)(THF), whereas solvent-free dialkyl derivatives Zr(eta(5):eta(1)-C(13)H(8)SiMe(2)NCMe(3))Ph(2) and Zr(eta(5):eta(1)-C13H8-SiMe(2)NCMe(3))(CH(2)SiMe(3) )2, all under preservation of the chelate structure, are obtained with PhMgCl and Me(3)SiCH(2)MgCl, respectively. Variable-temperature H-1 NMR spectroscopic data reveal a sterically congested ligand sphere around the zirconium atom which is confirmed by a single-crystal X-ray diffraction study in the case of the bis(trimethylsilylmethyl) derivative. The substituted fluorenyl ligand is pentahapto-bonded with some variation of the zirconium-ring carbon bond lengths. The amido nitrogen is trigonal planar as a result of significant pi-donatian to the zirconium. The two (trimethylsilyl)methyl groups do not appear to be strongly distorted despite being bound to a 12-electron d(0) center but give rise to a conformation in which the repulsion between the trimethylsilyl and the tert-butyl groups is minimized. This compound crystallizes from pentane in the monoclinic space group P2(1)/n with a = 9.326(3), b = 16.806(5), and c = 19.638(6) Angstrom, beta = 93.23(2)degrees, V = 3073(2) Angstrom(3), Z = 4,R = 0.0308, wR(2) = 0.079.

  DOI：

  10.1021/om00002a028