中国科学院机构知识库网格
Chinese Academy of Sciences Institutional Repositories Grid
Chloroyttrium 2-(1-(Arylimino)alkyl)quinolin-8-olate Complexes: Synthesis, Characterization, and Catalysis of the Ring-Opening Polymerization of epsilon-Caprolactone

文献类型:期刊论文

作者Zhang, Wenjuan2,3; Liu, Shaofeng2,3; Yang, Wenhong2,3; Hao, Xiang2,3; Glaser, Rainer1; Sun, Wen-Hua2,3
刊名ORGANOMETALLICS
出版日期2012-12-10
卷号31期号:23页码:8178-8188
ISSN号0276-7333
DOI10.1021/om300778g
英文摘要Stoichiometric reactions of YCl3(THF)(3) with potassium 2-(arylimino)methyl)quinolin-8-olates or 2-(1-(arylimino)ethyl)quinolin-8-olates in THF solution gave the mononuclear LYCl2(DMSO)(2) complexes 1-5 in the presence of DMSO and a representative dinuclear complex 6 in the absence of DMSO. All yttrium complexes were fully characterized by NMR measurements and elemental analysis, and the crystal structures of complexes 1 and 4-6 were determined by single-crystal X-ray diffraction. The structures indicate coordination number seven around the yttrium center and pentagonal bipyramidal geometries. The complexes all feature diapical YCl2 moieties and one tridentate organic ligand in the equatorial plane. Upon reaction of the yttrium precatalysts 1-6 with LiCH2Si(CH3)(3) alone or with LiCH2Si(CH3)(3) together with BnOH, the ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) occurred with high efficiency. Depending on conditions, the ROP of epsilon-CL produced polycaprolactone with narrow molecular distribution and in a living manner. Theoretical studies of the chlorine/CH2SiMe3 and Me3SiCH2/BnO ligand exchange reactions suggest that the replacement of the apical ligands can proceed without significantly affecting the equatorial ligands. These results suggest that one of the apical Y-CH2SiMe3 bonds within the LY(CH2SiMe3)(2) intermediate catalyzes the polymerization in the BnOH-free process. Most polymers generated by BnOH-assisted catalysis possess M-n values that are similar to M-n,M-cal values based on Y-OBn, suggesting that one apical Y-OBn bond of the diapical LY(OBn)(CH2SiMe3) intermediate catalyzes most or all of the ring polymerization of epsilon-CL.
语种英语
WOS记录号WOS:000312035500021
出版者AMER CHEMICAL SOC
源URL[http://ir.iccas.ac.cn/handle/121111/49287]  
专题中国科学院化学研究所
通讯作者Glaser, Rainer
作者单位1.Univ Missouri, Dept Chem, Columbia, MO 65211 USA
2.Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China
3.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
推荐引用方式
GB/T 7714
Zhang, Wenjuan,Liu, Shaofeng,Yang, Wenhong,et al. Chloroyttrium 2-(1-(Arylimino)alkyl)quinolin-8-olate Complexes: Synthesis, Characterization, and Catalysis of the Ring-Opening Polymerization of epsilon-Caprolactone[J]. ORGANOMETALLICS,2012,31(23):8178-8188.
APA Zhang, Wenjuan,Liu, Shaofeng,Yang, Wenhong,Hao, Xiang,Glaser, Rainer,&Sun, Wen-Hua.(2012).Chloroyttrium 2-(1-(Arylimino)alkyl)quinolin-8-olate Complexes: Synthesis, Characterization, and Catalysis of the Ring-Opening Polymerization of epsilon-Caprolactone.ORGANOMETALLICS,31(23),8178-8188.
MLA Zhang, Wenjuan,et al."Chloroyttrium 2-(1-(Arylimino)alkyl)quinolin-8-olate Complexes: Synthesis, Characterization, and Catalysis of the Ring-Opening Polymerization of epsilon-Caprolactone".ORGANOMETALLICS 31.23(2012):8178-8188.

入库方式: OAI收割

来源:化学研究所

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