桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

通过桥连双β-二酮类化合物与取代苯胺反应, 合成了5个新的桥连双(β-单酮亚胺)化合物(1~5)和2个新的桥连双(β-二酮亚胺)化合物(6,7), 它们与三甲基铝反应, 得到了相应的3个双(β-酮亚胺基)二铝配合物(8~10)和2个双(β-二酮亚胺基)二铝配合物(11,12). 采用核磁共振、 红外光谱和质谱等对这些化合物进行了表征, 通过X射线单晶衍射分析证实了铝配合物的结构, 并考察了这些铝配合物在ε-己内酯开环聚合反应中的催化活性.

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands†

Owing to its special physical and chemical properties as well as good coordination activity with transition metals, β-diketone-derived β-ketimines and β-diketimines have been extensively studied in recent years. In this work, five new bridged bis(β-ketimine)(1—5) and bis(β-diketimine) ligands(6,7) were synthesized by the condensation reaction of 3,3'-(1,4-phenylene)bis(2,4-pentanedione) with various anilines. Treatment of these ligands with AlMe₃ afforded five new aluminum complexes(8—12). All these compounds were characterized via elemental analysis, ¹H NMR, ¹³C NMR, ESI-MS and IR spectroscopy. Structures of two aluminium complexes were determined by the X-ray single-crystal diffraction analysis. The bridged β-ketimine acted as a chelating N, O-bidentate ligand to the aluminium atom. Each aluminum atom showed a distorted tetrahedral coordination geometry. These aluminum complexes exhibited effective catalytic activity in the ring-opening polymerization of ε-caprolactone.