Synthesis, Characterization, and Catalysis in ϵ-Caprolactone Polymerization of Aluminum and Zinc Complexes Supported by N,N,N-Chelate Ligands
Synthesis, Characterization, and Catalysis in ϵ-Caprolactone Polymerization of Aluminum and Zinc Complexes Supported by N,N,N-Chelate Ligands
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DOI：
10.1021/om701112m
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发表时间：
2008-03
期刊：
影响因子：
2.8
通讯作者：
Zuo-Yun Chai;Cheng Zhang;Zhong‐Xia Wang
中科院分区：
文献类型：
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作者：
Zuo-Yun Chai;Cheng Zhang;Zhong‐Xia Wang
合成并表征了一系列吡啶基N，N，N-螯合配体负载的铝、锌配合物。将2-(3，5-dimethyl-1H-pyrazol-1-yl)-6-((trimethylsilyl)methyl)pyridine(2)与LiBun/Tmeda反应，得到锂配合物[Li{2-(3，5-Me2C3HN2)-6-{N(SiMe3)C(Ph)═CH}C5H3N}]([LIL])(3)。3与氯化锌反应生成相应的氯化锌配合物[Zn(Cl)L](4)，再用甲基锂或乙基锂处理生成甲基或乙基锌配合物[Zn(R)L](R=Me，5a；R=Et，5b)。4与LiHBEt3反应生成乙基锌络合物(5b)。4与AlR3(R=Me，Et)反应生成烷基氯化铝配合物[Al(Cl)(R)L](R=Me，6a；R=Et，6b)。通过2-(3，5-Me_2C_3H_2)-6-{PhN-═P(Ph)_2CH_2}C_5H_3N(8)与锌的反应，得到了结构相似的N，N，N-螯合锌配合物。含[{2-{N(SiMe3)═P(Ph)2}-6-{N(SiMe3)P(Ph)2═CH}C5H3N}]−...的铝锌络合物
A series of aluminum and zinc complexes supported by pyridine-based N,N,N-chelate ligands have been synthesized and characterized. Treatment of 2-(3,5-dimethyl-1H-pyrazol-1-yl)-6-((trimethylsilyl)methyl)pyridine (2) with LiBun/tmeda and then PhCN afforded a lithium complex [Li{2-(3,5-Me2C3HN2)-6-{N(SiMe3)C(Ph)═CH}C5H3N}] ([LiL]) (3). Reaction of 3 with ZnCl2 formed corresponding zinc chloride complex [Zn(Cl)L] (4), which was transformed to methyl- or ethylzinc complex [Zn(R)L] (R = Me, 5a; R = Et, 5b) by treatment with methyl- or ethyllithium. The ethylzinc complex (5b) was also generated by reaction of 4 with LiHBEt3. Reaction of 4 with AlR3 (R = Me, Et) gave alkyl aluminum chloride complexes [Al(Cl)(R)L] (R = Me, 6a; R = Et, 6b). Structurally similar N,N,N-chelate zinc complex [Zn(Et){2-(3,5-Me2C3HN2)-6-{N(Ph)P(Ph2)═CH}C5H3N}] (9) was obtained by reaction of 2-(3,5-Me2C3HN2)-6-{PhN═P(Ph)2CH2}C5H3N (8) with ZnEt2. The aluminum and zinc complexes bearing [{2-{N(SiMe3)═P(Ph)2}-6-{N(SiMe3)P(Ph)2═CH}C5H3N}]−...