Synthesis, structure, and catalytic activity of organoaluminum complexes with chiral biaryl Schiff-base ligands

Synthesis, structure, and catalytic activity of organoaluminum complexes with chiral biaryl Schiff-base ligands
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手性联芳基希夫碱配体有机铝配合物的合成、结构和催化活性

DOI:
10.1016/j.ica.2014.01.009
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发表时间:
2014-03
影响因子:
2.8
通讯作者:
Zi, Guofu
Zi, Guofu
中科院分区:
化学3区
文献类型:
--
作者:
Wang, Qiuwen;Hou, Guohua;Song, Haibin;Zi, Guofu

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以(S)-2-氨基-2′-羟基-1,1′-联萘基和(S)-2-氨基-2′-羟基-6,6′-二甲基-1,1′-联苯基为原料,通过烷烃消去法制备了一系列新的有机铝配合物,产率较高。溶剂在铝配合物的形成中起着重要的作用。例如,用等量的alme3在THF中处理配体1h2,得到单核配合物(1)AlMe(THF)(8),产率为90%。而2h2、3H2、4H2、5H2、6h2或7h2与1等量的alme3在苯中反应,分别得到双核配合物{(2)AlMe}2(9)、{(3)AlMe}2(10)、{(4)AlMe}2(11)、{(5)AlMe}2(12)、{(6)AlMe}2(13)和{(7)AlMe}2(14),产率较高。配合物8 - 14已通过各种光谱技术、元素分析和x射线衍射分析进行了表征。配合物8 - 14是异丙醇存在下丙交酯聚合的活性催化剂,生成富杂交酯的聚丙交酯。
A new series of organoaluminum complexes have been prepared by alkane elimination in good yields from AlMe3and chiral biaryl Schiff-base NO2ligands,1H2-7H2, which are derived from (S)-2-amino-2′-hydroxy-1,1′-binaphthyl or (S)-2-amino-2′-hydroxy-6,6′-dimethyl-1,1′-biphenyl, respectively. However, solvent plays an important role in the formation of the aluminum complexes. For example, treatment of ligand1H2with 1 equiv of AlMe3in THF gives the mononuclear complex (1)AlMe(THF) (8) in 90% yield. While reaction of2H2,3H2,4H2,5H2,6H2or7H2with 1 equiv of AlMe3in benzene gives the binuclear complexes {(2)AlMe}2(9), {(3)AlMe}2(10), {(4)AlMe}2(11), {(5)AlMe}2(12), {(6)AlMe}2(13) and {(7)AlMe}2(14), respectively, in good yields. Complexes8–14have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. The complexes8–14are active catalysts for the polymerization ofrac-lactide in the presence of isopropanol, leading to the heterotactic-rich polylactides.
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