| Summary: | 碩士 === 國立彰化師範大學 === 化學系 === 101 === A series of aluminum, zinc and titanium complexes containing pyrrole-imine- pyridine ligand, [C4H3NH(2-CH=NCH2Py)], were synthesized and characterized. Treatment of 1 and 2 equiv of AlMe3 with pyrrole-imine-pyridine ligand, [C4H3NH(2-
CH=NCH2Py)], generates five-coordinated aluminum complex [Al{C4H3N(2-CH=N
CH2Py)}Me2] (1) and dialuminum complex [AlMe3{C4H3N(=CHNCH2Py)AlMe2}] (2). Further reacting of 1 and 2 equiv of 2,6-diisopropyphenol with 1 generate [Al{C4H3N(2-CH=NCH2Py)}Me-(O-2,6-iPr2C6H3)] (3) and [Al{C4H3N(2-CH=NCH2
Py)}(O-2,6-iPr2C6H3)2] (4), respectively. Similarly, Reacting 1 with 2 equiv of dibenzoylmethane, yields six-coordinated aluminum complex [Al{C4H3N(2-CH=N
CH2Py)}(PhCOCHCOPh)2] (5). While 1 or 2 equiv of benzyl alcohol and allyl alcohol used to react with 1, the C-C coupling products Al[{C4H3N(2-CH=N)CHPyCH(C4H3NH)NHCH2Py}(OCH2Ph)2] (6) and Al[{C4H3N(2-CH=N)CHPyCH(C4H3NH)NHCH2Py}(OCH2CH=CH2)2] (7) were isolated.
Treatment of 1 and 0.5 equiv of ZnEt2 with pyrrole-imine-pyridine ligand, [C4H3NH(2-CH=NCH2Py)], generates zinc complexes [Zn{C4H3N(2-CH=NCH2Py)}
Et]2 (8) and Zn{C4H3N(2-CH=NCH2Py)}2 (9). In addition, Ti{C4H3N(2-CH=NCH2
Py)}2(OiPr)2 (10) was obtained from the treatment of Ti(OiPr)4 with 2 equiv of [C4H3NH(2-CH=NCH2-Py)]. Reaction of 10 with 2 equiv of 2,6-dimethylphenol gave the complex [Ti{C4H3NH(2-CH=NCH2Py)}(O-2,6-Me2C6H3)2(μ-O)]2 (11).
All the aforementioned complexes have been characterized by 1H 、 13C NMR spectroscopy and have been determined by single crystal X-ray diffractometry in solid state. The aluminum complexes 1, 3, 4 and 5 were tested as initiators for the ring opening polymerization of ε-caprolactone and Meerwein-Ponndorf-Verley reaction.
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