Methylaluminium 8-quinolinolates: synthesis, characterization and use in ring-opening polymerization (ROP) of ε-caprolactone
作者:Wen-Hua Sun、Miao Shen、Wenjuan Zhang、Wei Huang、Shaofeng Liu、Carl Redshaw
DOI:10.1039/c0dt01207f
日期:——
The stoichiometric reactions of 2-(2,6-R-phenylimino)quinolin-8-ol (L1âL5, L1: R = Me, L2: R = Et, L3: R = iPr, L4: R = Cl, L5: R = F) with Me3Al afforded the dimeric aluminium complexes [Me2AlL]2 (1â5) in good yields. By contrast, stoichiometric reactions of 2-(1-(2,6-R-phenylimino)propyl) quinolin-8-ol (L6âL10, L6: R = Me, L7: R = Et, L8: R = iPr, L9: R = Cl, L10: R = F)) with Me3Al gave the mononuclear aluminium complexes Me2AlL (6â10) accompanied with by-products of the form Me2AlL·Me3Al (11â15). All methylaluminium complexes were characterized by NMR spectroscopy, elemental analysis, and the molecular structures of complexes 3, 6 and 8 were determined by single-crystal X-ray diffraction. Aluminium compounds 1â5 possessed negligible activity towards the ring-opening polymerization of ε-caprolactone either in the presence or absence of BnOH. In contrast, in the presence of BnOH, the mononuclear aluminium compounds 6â10 could efficiently initiate the ring-opening polymerization of ε-caprolactone; the polymerization proceeded in a living manner.
2-(2,6-R苯基亚氨基)喹啉-8-醇(L1~L5, L1: R = Me, L2: R = Et, L3: R = iPr, L4: R = Cl, L5: R = F)与Me3Al的化学计量反应以良好收率得到了二聚体铝配合物[Me2AlL]2 (1~5)。相比之下,2-(1-(2,6-R-苯基亚氨基)丙基)喹啉-8-醇(L6~L10, L6: R = Me, L7: R = Et, L8: R = iPr, L9: R = Cl, L10: R = F)与Me3Al的化学计量反应得到了单核铝配合物Me2AlL (6~10),同时伴随着副产物Me2AlL·Me3Al (11~15)的生成。所有甲基铝配合物均通过NMR光谱、元素分析进行了表征,配合物3、6和8的分子结构由单晶X射线衍射确定。铝化合物1~5对ε-己内酯的开环聚合无论有无BnOH的存在均无活性。相反,在BnOH存在下,单核铝化合物6~10能高效引发ε-己内酯的开环聚合;聚合过程表现出生长方式。