A series of novel binuclear phenoxyimino organoaluminum complexes of the type [(RNCH)C6H3OAlMe2]2 [R = C6H5 (2a), 2,6-iPr2C6H3 (2b), 2,6-Ph2C6H3 (2c), adamantyl (2d), tBu (2e)] have been prepared in high yields, and these complexes were identified by 1H, 13C NMR and elemental analysis. Structural analysis for 2aâe revealed that these complexes have a distorted tetrahedral geometry around Al and both the AlâO and the AlâN bond distances were considerably influenced by substituents in the imino groups. The complexes were tested as catalyst precursors for ring-opening polymerisation (ROP) of ε-caprolactone (CL) in the presence of BnOH, and their catalytic activities were strongly affected by the catalyst structures and polymerisation conditions. An efficient living ROP has been achieved using the 2b/BnOH system.
高产率制备了一系列新型双核苯氧基亚
氨基
有机铝配合物[(RNCH)
C6H3OAlMe2]2 [R =
C6H5 (2a)、2,6-iPr2 (2b)、2,6-Ph2 (2c)、
金刚烷基 (2d)、tBu (2e)],并通过 1H、13C NMR 和元素分析对这些配合物进行了鉴定。2aâe 的结构分析表明,这些配合物在 Al 周围具有扭曲的四面体几何形状,AlâO 和 AlâN 键的距离受到亚
氨基中取代基的很大影响。这些配合物被用作催化剂前体,在 BnOH 存在下进行
δ-己内酯(CL)的开环聚合(ROP)试验,其催化活性受到催化剂结构和聚合条件的强烈影响。利用 2b/BnOH 体系实现了高效的活 ROP。