Abstract
Coupling of CO2 with epoxides is a green emerging alternative for the synthesis of cyclic organic carbonates (COC) and aliphatic polycarbonates (APC). The scope of this work is to provide a comprehensive overview of metal complexes having sulfur-containing ligands as homogeneous catalytic systems able to efficiently promote this transformation with a concise discussion of the most significant results. The crucial role of sulfur as the hemilabile ligand and its influence on the catalytic activity are highlighted as well.
Highlights
Homogeneous catalysis is one of the most fast-developing areas of chemistry because of the possibility to finely tune the course of a given reaction by rational design of the catalyst architecture
An in situ IR spectroscopy study showed that, in the early stages, only the cyclic organic carbonates (COC) was formed by complexes 5 and 6, whereas the production of the aliphatic polycarbonates (APC) started after 50 min
This was coherent with the experimental observation that the course of the reaction can be driven to the formation of PC or PPC by a proper choice of the reaction conditions
Summary
Homogeneous catalysis is one of the most fast-developing areas of chemistry because of the possibility to finely tune the course of a given reaction by rational design of the catalyst architecture. In inthese thesespecies, species,the thestrength strengthof ofthe theinteraction interactionbetween betweenthe themetal metalcenter centerand and the the donor donor In these species, the strength of the interaction between the metal center and the donor atoms can be scarcely modulated because of the hard nature of nitrogen as a Lewis base. In this review,and we copolymerization cover the recent progress the use of the corresponding Despite these findings, the use of sulfur-based ligands in the 2CO2/epoxide coupling has been metal complexes in theby cycloaddition and copolymerization of CO and epoxides, evidencing the fundamental role played the ligand framework in modulating the catalytic efficiency. Metal complexes in the cycloaddition and copolymerization of CO2 and epoxides, evidencing the fundamental role played by the ligand framework in modulating the catalytic efficiency. Metal Complexes Bearing Sulfur-Containing Ligands Active in the Coupling of CO2
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