Acrylate synthesis from carbon dioxide - ethylene coupling catalyzed by first-row transition metal complexes
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Carbon dioxide (CO₂) is an abundant and renewable carbon source than can be used as feedstock for the synthesis of value-added materials. One such material is acrylic acid, and acrylate derivatives, which can be used in the production of super absorbent polymers, adhesives, and coatings. The oxidative coupling of CO₂ and ethylene offers a more atom-economical and sustainable approach acrylic acid formation relative to the petroleum-based synthesis currently in use. This dissertation examines the ability of the first-row transition metals Nickel (Ni) and Iron (Fe) to yield acrylate from CO₂ and ethylene. A wealth of research on Ni-mediated CO₂-ethylene coupling reactions laid the groundwork for a variety of in-depth investigations into ancillary ligand effects and the role of additives in the multi-component system. Moderate improvements to catalytic activity were observed but ultimately the progress of this system has stalled, and investigations turned to the development of novel Fe complexes. A family of low valent Fe complexes were found to facilitate CO₂-ethylene coupling. However, the insertion of two CO₂ units was observed, resulting in the formation of the dicarboxylate product methylmalonic acid (MMA). A one electron oxidation was found to slow the rate of second CO₂ insertion and mixtures of propionic acid (PA) and MMA were obtained.
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Ph. D.