| 222713-94-2

• CAS: 222713-94-2
• 化学式: C₄₀H₄₂Cl₂N₄Si₂Zr
• 分子量: 797.101
• InChiKey: JYAMMZRTJMYEMZ-KKFJYKEPSA-L

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

• 作为产物：
  描述：

  、 氯化锆(IV) 以 乙醚 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  Novel monoanionic di-N,N′-centred chelating ligands and their C1 and C2 symmetrical zirconium complexes

  摘要：

  The novel lithium complexes [Li{N(SiMe(3))C(Ph)C(R)(C5H4N-2)}](2) (R = H or SiMe(3)) and Li{N(SiMe(3))C(Ph)C(R)(C9H6N-2)} (R = H or SiMe(3)), prepared from PhCN and [Li{C(SiMe(3))(R)(C5H4N-2)}](2) or Li{C(SiMe(3))(R)(C9H6N-2)}, react with ZrCl4 to afford racemic complexes [Zr{N(SiMe(3))C(Ph)C(R)(C5H4N-2)}Cl-2(2)] (R = H or SiMe(3), 3b) and [Zr{N(SiMe(3))C(Ph)C(R)(C9H4N-2)}Cl-2(2)], respectively. Conproportionation of ZrCl4 and 3b or 4b afforded [Zr{N(SiMe(3))C(Ph)C(SiMe(3))(C5H4N-2)}Cl-3] and [Zr{N(SiMe(3))C(Ph)C(SiMe(3))(C9H6N-2)}Cl-3], respectively. The compounds are characterised by NMR spectroscopy and X-ray data are provided for 3b.

  DOI：

  10.1016/0022-328x(95)06108-9

文献信息

• Novel Zirconium and Hafnium Complexes of Monoanionic Di-<i>N</i>,<i>N</i>‘-chelating Pyridyl- and Quinolyl-1-azaallyl Ligands and Their Activity in Olefin Polymerization Catalysis
  作者：Berth-Jan Deelman、Peter B. Hitchcock、Michael F. Lappert、Wing-Por Leung、Hung-Kay Lee、Thomas C. W. Mak

  DOI：10.1021/om980850b

  日期：1999.4.1

  The lithium complexes [LiN(SiMe3)C(R-1)C(R-2)(C5H4N-2)}](2) (1a, 2a, and 3a) were each treated with MCl4 to afford the racemic complexes [MN(SiMe3)C(R-1)C(R-2)(C5H4N-2)}(2)Cl-2] (M = Zr, R-1 = Ph, R-2 = H (1b); M = Zr, R-1 = Bu-t, R-2 = H (2b); M = Hf, R-1 = Bu-t, R-2 = H (2c); M = Zr, R-1 = Ph, R-2 = SiMe3 (3b)). Similarly, LiN(SiMe3)C(Ph)C(R)(C9H6N-2)} (4a and 5a) afforded the racemic complexes [ZrN(SiMe3)C(Ph)C(R)(C9H6N-2)}(2)Cl-2] (R = H (4b); R = SiMe3 (5b)). X-ray structural analysis of 2b, 2c, and 3b revealed that these complexes have C-2 octahedral geometries with their chloride ligands in cis positions. Molecular orbital calculations on model systems of the bis3-(2-pyridyl)-1-azaallyl}zirconium system [Zr(LL)(2)](2+) (LL = (N(H)C(H)C(H)(2-C5H4N]) demonstrate that (i) the frontier orbitals are similar to those of [Zr(eta(5)-C5H5)(2)](2+) and (ii) the bis3-(2-pyridyl)-1-azaallyl} ligand environment is more electron-donating, making the zirconium system less electrophilic. Conproportionation of ZrCl4 with [ZrN(SiMe3)C(R-1)C(R-2)(C5H4N-2)}(2)Cl-2] or [ZrN(SiMe3)C(Ph)C(SiMe3)(C9H6N-2)}(2)Cl-2] afforded the mono(1-azaallyl)zirconium complexes ZrN(SiMe3)C(R-1)C(R-2)(C5H4N-2)}Cl-3 (R-1 = Bu-t, R-2 = H (2d); R-1 = Ph, R-2 = SiMe3 (3d)) and ZrN(SiMe3)C(Ph)C(SiMe3)(C9H6N-2)}Cl-3 (5d), respectively. When activated with methylaluminoxane (MAO), these compounds were highly active in ethylene polymerization. Compound 3d also showed modest activity in the polymerization of 1-hexene and the copolymerization of ethylene and 1-hexene.