Structure-activity relationships of homogeneous Pd species in high-pressure diene-CO2 reactions forming carbon-fixating monomers

This proposal aims to shed light on the Pd-catalyzed reaction of novel conjugated dienes with CO2. Recently, several new dienes were synthesized in our group, widening the potential scope of this reaction. The synthesis of cyclic monoesters with these dienes would provide a wide variety of building blocks for polyesters with high CO2 fixation capacity. To achieve high product yields for different types of dienes, more insights in (i) the catalytic cycle, (ii) structure-activity relationships and (iii) the main deactivation routes are required. These aspects have not yet been properly investigated using relevant characterization techniques (e.g. XAS, NMR, IR) due to the challenging reactions conditions, such as high CO2 pressure. The proposed experiment aims to fill this gap, focusing on the characterization of the Pd catalysts under industrially relevant temperature and CO2 pressure, employing an ad hoc designed high-pressure catalytic cell.