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Please use this identifier to cite or link to this item: http://ir.ncue.edu.tw/ir/handle/987654321/14796

Title: Zirconium and Hafnium Amide, Alkoxide, and Pyrrolyl Complexes Manifesting with Pyrrolyl-linked N-donor Ligands: Syntheses, Characterization, and Ring Opening Polymerization of ε-caprolactone
Authors: Lee, Wen-Yi;Hsieh, Chun-Chin;Hsu, Jia-Wei;Datta, Amitabha;Lin, Yu-Chun;Huang, Jui-Hsien;Lee, Ting-Yu
Contributors: 化學系
Keywords: Zirconium;Hafnium;Alkoxide;Pyrrole;Ring opening polymerization
Date: 2011-11
Issue Date: 2012-12-10T01:40:11Z
Publisher: Elsevier
Abstract: A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5-CH2NMe2)2] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH2NMe2)2] with M(NEt2)4 (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe2)2]M(NEt2)3 (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH2NMe2)2]M(NEt2)3 with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H2N(2,5-CH2NMe2)2]M(OC6H3-2,6-tBu2)(NEt2)2 (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH2NMe2)2]M(OtBu)3 (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe2)2]M(C4H4N)3 (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3–8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84–2.75) representing multiple reactivity centers of these complexes.
Relation: Journal of Organometallic Chemistry, 696(23): 3816-3821
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