[(OC6H2(t-Bu)2C(N-i-Pr)2)ZrCl]3(μ3-O)(μ3-Cl) | 1366043-84-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [(OC6H2(t-Bu)2C(N-i-Pr)2)ZrCl]3(μ3-O)(μ3-Cl)
• 英文别名: 2,4-ditert-butyl-6-(N-propan-2-yl-C-propan-2-ylazanidylcarbonimidoyl)phenolate;oxygen(2-);zirconium(4+);tetrachloride
• CAS: 1366043-84-6
• 化学式: C₆₃H₁₀₂Cl₄N₆O₄Zr₃
• 分子量: 1423.02
• InChiKey: JXMGCRPXTPPCKY-UHFFFAOYSA-G

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  80
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 (4,6-(t-Bu)2C6H2O-2-C(N(i-Pr))N(i-Pr))H2 在 n-BuLi 作用下， 以 乙醚 为溶剂， 以11%的产率得到[(OC6H2(t-Bu)2C(N-i-Pr)2)ZrCl]3(μ3-O)(μ3-Cl)
  参考文献：
  名称：

  Synthesis and Structural Diversity of Group 4 Metal Complexes with Multidentate Tethered Phenoxy-Amidine and Phenoxy-Amidinate Ligands

  摘要：

  The coordination chemistry of the multidentate tethered amidine-phenol {4,6-tBu(2)C(6)H(2)O (2-C(NR)=NR}H-2 ({LONR}H-2, R = iPr, 2,6-iPr(2)C(6)H(3) (Ar)) and new guanidine-phenol {4,6-tBu(2)C(6)H(2)ON(C6H3)(2-C(NR)=NR}H-2 ({LON(Ph)N-iPr}H-2) pro-ligands with group 4 metals has been studied. sigma-Bond and salt metathesis reactions were explored to coordinate these (pro)ligands onto zirconium and hafnium. Alkane elimination reactions between {LONR}H-2 and Zr(CH2Ph)(4) afforded mixed-ligand monobenzyl {(LONR)-N-H}{LONR}Zr(CH2Ph) (R = iPr; 1) and monoligand tribenzyl {(LONAr)-N-H}Zr(CH2Ph)(3) (R = Ar; 2) complexes, respectively. Alkane and amine elimination reactions between {LON(Ph)N-iPr}H-2 and Zr(CH2Ph)(4) or Hf(NMe2)(4) unexpectedly resulted in cleavage of the ligand backbone and eventual isolation of {(Ph)NC6H2(tBu)(2)O}Zr{(iPrN)(2)CCH2Ph}(2) (3) and {(Ph)NC6H2(tBu)(2)O}Hf{(iPrN)(2)CNMe2}(2) (4), respectively. Salt metathesis reactions between {LONR}Li-2 and ZrCl4(THF)(n) (n = 0, 2), conducted in 1:1 ratios, led upon crystallization to diverse chloro complexes: [{LONiPr}ZrCl](3)(mu(3)-O)(mu(3)-Cl) (5), {{LONAr}(2)ZrCl(mu(2)-Cl)](2)[{(LONAr)-O-H}ZrCl(mu(2)-Cl)](mu(3)-OH) (6), and {(LONAr)-N-H}ZrCl3(THF) (7). Similar salt metathesis reactions between the monolithium salts {(LONR)-O-H}Li and ZrCl4, conducted in 2:1 ratios, allowed the selective preparation of bis(phenoxy-amidine) complexes with pendant amino groups {(LONR)-N-H}(2)ZrCl2 (R = iPr, 8; R = Ar, 9). All complexes were authenticated by elemental analysis, X-ray crystallography, and NMR spectroscopy. Complexes 5, 6, 8, and 9, upon activation with MAO, showed poor to moderate productivities (4-172 (kg of PE) mol(-1) h(-1)) in the polymerization of ethylene, giving linear polymers with large polydispersities.

  DOI：

  10.1021/om300076j