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Title: Synthesis and Characterization of Zirconium and Hafnium Aryloxide Compounds and Their Reactivity Towards Lactide and ϵ-Caprolactone Polymerization
Authors: Hsieh, Kun-Chun;Lee, Wen-Yi;Hsueh, Li-Feng;Lee, Hon-Man;Huang, Jui-Hsien
Contributors: 化學系
Keywords: Hafnium aryloxide;Zirconium aryloxide;Lactide;Caprolactone;Hafnium;Zirconium
Date: 2006-06
Issue Date: 2012-12-10T01:39:45Z
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Abstract: Reactions of 2 equiv. pyrrole with [C4H3N(CH2NMe2)-2]2M(NEt2)2 in toluene generated tetra-pyrrolyl metal compounds [C4H3N(CH2NMe2)-2]2M(C4H4N)2 (3, M = Zr; 4, M = Hf) in moderate yields. Similarly, treatment of metal amides [C4H3N(CH2NMe2)-2]2M(NEt2)2 with 2,6-dimethylphenol or 2,6-diisopropylphenol in heptane resulted in the elimination of diethylamine along with the formation of the corresponding metal alkoxides [C4H3N(CH2NMe2)-2]2M(OR)2 (5, M = Zr, R = C6H3-2,6-Me2; 6, M = Hf, R = C6H3-2,6-Me2; 7, M = Zr, R = C6H3-2,6-iPr2; 8, M = Hf, R = C6H3-2,6-iPr2) in moderate yields. All the new compounds were characterized by 1H and 13C NMR spectroscopy and the structures of 3, 4, 6, 7, and 8 have also been determined by X-ray crystallographic studies. The aryloxides and the substituted pyrrolyl ligands in both compounds 5 and 6 show fluxionality as observed by 1H NMR signals. A kinetic study on the ring-opening polymerization of lactide exhibits a first-order reaction of lactide monomer with compound 8. The catalytic properties of all the metal complexes have been studied for the ring-opening polymerization of ϵ-caprolactone.
Relation: European Journal of Inorganic Chemistry, 2006(11): 2306-2312
Appears in Collections:[化學系] 期刊論文

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