State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
Dalton Trans. 2013 Sep 14;42(34):12346-53. doi: 10.1039/c3dt50264c. Epub 2013 Jul 17.
A series of novel binuclear phenoxyimino organoaluminum complexes of the type [(RN=CH)C6H3OAlMe2]2 [R = C6H5 (2a), 2,6-(i)Pr2C6H3 (2b), 2,6-Ph2C6H3 (2c), adamantyl (2d), (t)Bu (2e)] have been prepared in high yields, and these complexes were identified by (1)H, (13)C NMR and elemental analysis. Structural analysis for 2a-e revealed that these complexes have a distorted tetrahedral geometry around Al and both the Al-O and the Al-N 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.
一系列新型双核苯氧基亚氨基有机铝配合物[(RN=CH)C6H3OAlMe2]2（R = C6H5（2a），2,6-（i）Pr2C6H3（2b），2,6-Ph2C6H3（2c），金刚烷基（2d），（t）Bu（2e））已以高产率制备，这些配合物通过（1）H，（13）C NMR 和元素分析进行了鉴定。对 2a-e 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，并且亚氨基中的取代基对 Al-O 和 Al-N 键的距离都有很大的影响。这些配合物被测试为在 BnOH 存在下ε-己内酯（CL）开环聚合（ROP）的催化剂前体，其催化活性受到催化剂结构和聚合条件的强烈影响。使用 2b/BnOH 体系实现了有效的活性 ROP。
