期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 689, 期 5, 页码 971-979出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2003.12.030
关键词
online ATR-IR spectroscopy; catalytic carbonylation; epoxides; lactones; aliphatic polyesters
In situ ATR-IR spectroscopy is applied as a powerful tool to study the factors that control the reaction of epoxides with carbon monoxide in the presence of [Lewis acid](+)[Co(CO)(4)](-) salts. Based on these investigations, a consistent mechanistic scheme is presented, comprising the main lactone and polyester products and minor components, e.g., acetone and crotonic acid derivatives. beta-Alkoxy-acyl-cobalttetracarbonyl species are shown to be key intermediates from which two reaction routes start in dependence of the applied Lewis acid (LA). Labile LA-alkoxy combinations favor a backbiting process of the oxygen function on the Co-acyl bond, primarily producing lactone products. More stable LA-alkoxy entities are unreactive toward PO conversion and afford a polymerization reaction after the addition of a nucleophile. In that case, the Lewis acid remains bonded to the chain end. (C) 2004 Elsevier B.V. All rights reserved.
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