Facile estimation of catalytic activity and selectivities in copolymerization of propylene oxide with carbon dioxide mediated by metal complexes with planar tetradentate ligand.

Mechanistic studies were conducted to estimate (1) catalytic activity for PPC, (2) PPC/CPC selectivity, and (3) PPC/PPO selectivity for the metal-catalyzed copolymerization of propylene oxide with carbon dioxide [PPC: poly(propylene carbonate); CPC = cyclic propylene carbonate; PPO: poly(propylene oxide)]. Density functional theory (DFT) studies demonstrated that the ΔG(crb) - ΔG(epx) value should be an effective indicator for the catalytic activities [ΔG(epx): dissociation energy of ethylene oxide from the epoxide-coordinating metal complex; ΔG(crb): dissociation energy of methyl carbonate from the metal-carbonate complex]. In addition, metal complexes with a subthreshold ΔG(epx) value were found to show low PPC/CPC selectivity.

Manganese-corrole complexes as versatile catalysts for the ring-opening homo- and co-polymerization of epoxide.

Manganese-corrole complexes in combination with a co-catalyst [PPN]X ([PPN](+)=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO2, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.

Copolymerization of epoxides with carbon dioxide catalyzed by iron-corrole complexes: synthesis of a crystalline copolymer.

Iron-corrole complexes were found to copolymerize epoxides with CO2. The first iron-catalyzed propylene oxide/CO2 copolymerization has been accomplished. Moreover, the glycidyl phenyl ether (GPE)/CO2 copolymerization with this catalyst provided a crystalline material as a result of the isotactic poly(GPE) moiety.