rac-(1,12-bis(tetrahydroindenyl)dodecanyl)dimethylzirconium | 155737-08-9

• 英文名称: rac-(1,12-bis(tetrahydroindenyl)dodecanyl)dimethylzirconium
• CAS: 155737-08-9
• 化学式: C₃₂H₅₀Zr
• 分子量: 525.973
• InChiKey: GOVDWMFNCLNPSW-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  rac-(1,12-bis(tetrahydroindenyl)dodecanyl)zirconium dichloride 在 CH₃Li 作用下， 以 乙醚 、 甲苯 为溶剂， 以71%的产率得到rac-(1,12-bis(tetrahydroindenyl)dodecanyl)dimethylzirconium
  参考文献：
  名称：

  Formation and Structure of a Novel Large-Ring Group 4 ansa-Metallocene Complex

  摘要：

  1,12-Dodecanediol was treated with 2 molar equiv of methanesulfonyl chloride and then with indenyllithium to yield 1,12-bis(3-indenyl)dodecane (4). Double deprotonation of 4 with n-butyllithium gave the corresponding dilithio compound 5. Its reaction with ZrCl4(THF)2 in tetrahydrofuran under high dilution conditions gave the large-ring ansa-metallocene dihalide complex rac-6 in 15% isolated yield. Under similar conditions the reaction of 5 with ZrCl4(THF) 2 in toluene solvent allowed the isolation of the diastereoisomer meso-6 in 11% yield. The complex rac-6 was hydrogenated to yield the corresponding large-ring ansa-bis(tetrahydroindenyl)zirconium dichloride complex rac-8. Each of the complexes rac-6, meso-6, and rac-8 reacted cleanly with methyllithium to yield the corresponding ansa-metallocene dimethyl derivatives (rac-7, meso-7, rac-9). The organic compound 4 and the ansa-metallocene rac-6 were characterized by X-ray diffraction. In the solid state the metallocene precursor 4 exhibits a (-CH2-)12 chain at its maximal elongation, which separates the indenyl end groups intramolecularly as far as possible. In the large-ring ansa-metallocene dichloride complex rac-6 the 1,12-dodecanediyl chain that connects the two eta5-indenyl ligands is oriented in a nearly C2-symmetric arrangement in the central position in front of the bent-metallocene wedge. In this orientation the mean plane of the (-CH2-)12 loop is arranged orthogonal to the ZrCl2 sigma-ligand plane and spatially separates the two segments in front of the bent-metallocene unit where the reactive sigma-ligands are located.

  DOI：

  10.1021/om00017a060