Transition metal mediated coupling of carbon dioxide and ethene to acrylic acid/acrylates

The search for renewable alternative energy sources and energy storing possibilities has gained significant importance during the last decades, due to depleting fossil carbon sources, the continuously increasing human population and a generally increasing interest in environmental issues. Carbon dioxide, for example, can be captured directly at its source and thus made available for chemical industry. Homogeneous catalysis in solution is an attractive alternative to established heterogeneous procedures to utilize the C-1 building block CO2 as an abundant and cheap starting material. Therefore, the development of cost efficient routes to bulk chemicals like acrylic acid and acrylates has significant interest for industry. In order to progress more rapidly in such a research field a combination of experiment and computational calculations is often considered as beneficial. This review presents a comprehensive overview on the synthesis of acrylates and acrylic acid, starting from CO2, focusing on synthetic insights as well as current findings in theoretical studies. Mechanistic studies are outlined and rational approaches to a full catalytic cycle presented using various molecular transition metal catalysts. In addition, the first catalytic transformations of carbon dioxide and ethene to acrylic acid are presented. (C) 2015 Elsevier B.V. All rights reserved.