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Title: Aluminum Compounds Containing η1- and/or η5-Bidentate Dianionic Pyrrolyl–Methylamide Ligands
Authors: Chen, Ya-Chi;Lin, Che-Yu;Li, Chun-Yin;Huang, Jui-Hsien;Chang, Ling-Chueh;Lee, Ting-Yu
Contributors: 化學系
Keywords: Aluminum;Caprolactone;Lithium;Ring-opening polymerization;Sandwich complexes
Date: 2008-10
Issue Date: 2012-12-10T01:39:52Z
Publisher: WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Abstract: A series of dialuminum compounds have been synthesized and their reactivity and application for lactide polymerization have been studied. The reaction of AlH3⋅NMe3 with [C4H3NH(2-CH2NHtBu)] in diethyl ether generated a dimeric aluminum hydride compound, [{[C4H3N(2-CH2NtBu)]AlH}2] (1). The structure of 1 was confirmed by spectroscopy of a deuterated analogue of 1 with an AlD function. Direct treatment of [C4H3NH(2-CH2NHtBu)] with LiAlH4 in diethyl ether resulted in colorless crystals of [{Li[μ-η1:η5-C4H3N(2-CH2NtBu)]2Al}2] (2) in 80 % yield after recrystallization from a toluene solution. The μ-η1:η5-pyrrolyl protons exhibit high-field shifts at δ=5.73, 6.15, and 6.72 comparable to a similar η5-bonding mode in the literature. Treatment of 1 with 1 equiv acetone oxime or acetone in dichloromethane gave [{[C4H3N(2-CH2NtBu)]Al[ϰO,ϰN-(ONCMe2)]}2] (3) and [{[C4H3N(2-CH2NtBu)]Al(OCHMe2)}2] (4) in 67 % and 60 % yield, respectively. Compounds 1–4 have been characterized by X-ray diffractometry and were used as catalysts for ε-caprolactone polymerization.
Relation: Chemistry--A European Journal, 14(31): 9747-9753
Appears in Collections:[Department of Chemistry] Periodical Articles

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