[N,N'-(1,2-dimethyl-1,2-ethanediylidene)(3,5-bis(benzofuran-2-yl)phenyl)amine][η3-2-propenyl]nickel hexafluoroantimonate | 724428-42-6

• 英文名称: [N,N'-(1,2-dimethyl-1,2-ethanediylidene)(3,5-bis(benzofuran-2-yl)phenyl)amine][η3-2-propenyl]nickel hexafluoroantimonate
• CAS: 724428-42-6
• 化学式: C₅₁H₃₇N₂NiO₄*F₆Sb
• 分子量: 1036.3
• InChiKey: GYVKLXPZOXINKH-HSPRDOGCSA-H

反应信息

• 作为产物：
  描述：

  silver hexafluoroantimonate 、 bis-allylnickel chloride 、 2,3-bis(2,6-bis(benzofuran-2-yl)phenylimino)butane 以 乙醚 为溶剂， 以85%的产率得到[N,N'-(1,2-dimethyl-1,2-ethanediylidene)(3,5-bis(benzofuran-2-yl)phenyl)amine][η3-2-propenyl]nickel hexafluoroantimonate
  参考文献：
  名称：

  ortho-5-Methylfuran- and Benzofuran-Substituted η³-Allyl(α-diimine)nickel(II) Complexes:  Syntheses, Structural Characterization, and the First Polymerization Results

  摘要：

  Two representatives of a new family of ortho-furan-substituted N,N-phenyl alpha-diimine ligands [(Ar-N=C(Me)-(Me)C=N-Ar) Ar = 2,6-bis(5-methylfuran-2-yl)-4-phenylphenyl, 9; Ar = 2,6-bis(benzofuran-2-yl)phenyl, 171 have been synthesized by two alternative synthetic methodologies. 3,5-Bis(5-methylfuran-2-yl)biphenyl-4-ylamine (7) was prepared through a classical pyrylium salt approach. 2,6-Bis(5-methylfuran-2-yl)-4-phenylpyranylium tetrafluoroborate (4) was converted to 2,6-bis(5-methylfuran-2-yl)-4-phenylnitrobenzene (5) by reaction with nitromethane. Reduction of nitro compound 5 by zinc dust afforded aniline 7. The palladium-catalyzed cross-coupling reaction between 2,6-dibromophenylamine 13 and 2-benzofuranboronic acid 14 was used to prepare 2,6-bis(benzofuran-2-yl)phenylamine 15. The condensation of 2,2,3,3-tetramethoxybutane 8 with anilines 7 and 15 afforded alpha-diimines 9 and 17. The reaction of pi-allylnickel chloride dimer 10, alpha-diimines 9 and 17, and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAF) (11) or silver hexafluoroantimonate 18 led to three complexes, [eta(3)-allyl(Ar-N=C(Me)-(Me)C=N-Ar)Ni]X-+(-) [Ar = 2,6-bis(5-methylfuran-2-yl)-4-phenylphenyl, X = BAF, 12, Ar = 2,6-bis(benzofuran-2-yl)phenyl, X = BAF, 19, X = SbF6, 20]. The steric repulsion of closely positioned benzofuran-2-yl groups in 20 caused distortion of the nickel square planar coordination by up to 11.4degrees according to X-ray analysis. Benzofuran-2-yl groups deviated up to 46.6degrees from the main planes of central phenyl rings in 20. Complexes 12 and 19 were tested as ethylene polymerization catalysts. The benzofuran-substituted eta(3)-allyl (alpha-diimine)NI complexes 19 afforded polyethylene with ultrahigh molecular weights (M-w) and was about three time more productive than complex 12.

  DOI：

  10.1021/om0497902