The use of carbon dioxide as a carbon source for the synthesis of organic chemicals can contribute to a more sustainable chemical industry. Because CO(2) is such a thermodynamically stable molecule, few effective catalysts are available to facilitate this transformation. Currently, the major industrial processes that convert CO(2) into viable products generate urea and hydroxybenzoic acid. One of the most promising new technologies for the use of this abundant, inexpensive, and nontoxic renewable resource is the alternating copolymerization of CO(2) and epoxides to provide biodegradable polycarbonates, which are highly valuable polymeric materials. Because this process often generates byproducts, such as polyether or ether linkages randomly dispersed within the polycarbonate chains and/or the more thermodynamically stable cyclic carbonates, the choice of catalyst is critical for selectively obtaining the expected product. In this Account, we outline our efforts to develop highly active Co(III)-based catalysts for the selective production of polycarbonates from the alternating copolymerization of CO(2) with epoxides. Binary systems consisting of simple (salen)Co(III)X and a nucleophilic cocatalyst exhibited high activity under mild conditions even at 0.1 MPa CO(2) pressure and afforded copolymers with >99% carbonate linkages and a high regiochemical control (∼95% head-to-tail content). Discrete, one-component (salen)Co(III)X complexes bearing an appended quaternary ammonium salt or sterically hindered Lewis base showed excellent activity in the selectively alternating copolymerization of CO(2) with both aliphatic epoxides and cyclohexene oxide at high temperatures with low catalyst loading and/or low pressures of CO(2). Binary or one-component catalysts based on unsymmetric multichiral Co(III) complexes facilitated the efficient enantioselective copolymerization of CO(2) with epoxides, providing aliphatic polycarbonates with >99% head-to-tail content. These systems were also very efficient in catalyzing the terpolymerization of cyclohexene oxide, propylene oxide and CO(2). The resulting terpolymer had a single glass-transition temperature and a single thermolysis peak. This Account also provides a thorough mechanistic understanding of the high activities, excellent selectivities, and unprecedented stereochemical control of these Co(III)-based catalysts in the production of CO(2) copolymers . The catalysis occurs through a cooperative monometallic mechanism, in which the Lewis acidic Co(III) ion serves as electrophile to activate then epoxide and the nucleophilic counterion or cocatalyst serves as a nucleophile to initiate polymer-chain growth. The high activity and excellent regioselectivity observed in the epoxide ring-opening reactions results from epoxide activation through the moderate electrophilicity of the Co(III) ion, the fast insertion of CO(2) into the Co-O bond, and the facile dissociation of the propagating carboxylate species from the central metal ion. The reversible intra- or intermolecular Co-O b...

The mechanism of the copolymerization of CO(2) and epoxides to afford the corresponding polycarbonates catalyzed by a highly active and thermally stable cobalt(III) complex with 1,5,7-triabicyclo[4,4,0] dec-5-ene (designated as TBD, a sterically hindered organic base) anchored on the ligand framework has been studied by means of electrospray ionization mass spectrometry (ESI-MS) and Fourier transform infrared spectroscopy (FTIR). The single-site, cobalt-based catalyst exhibited excellent activity and selectivity for polymer formation during CO(2)/propylene oxide (PO) copolymerization even at temperatures up to 100 degrees C and high [epoxide]/[catalyst] ratios, and/or low CO(2) pressures. The anchored TBD on the ligand framework plays an important role in maintaining thermal stability and high activity of the catalyst. ESI-MS and FTIR studies, in combination with some control experiments, confirmed the formation of the carboxylate intermediate with regard to the anchored TBD on the catalyst ligand framework. This analysis demonstrated that the formed carboxylate intermediate helped to stabilize the active Co(III) species against decomposition to inactive Co(II) by reversibly intramolecular Co-O bond formation and dissociation. Previous studies of binary catalyst systems based on Co(III)-Salen complexes did not address the role of these nucleophilic cocatalysts in stabilizing active Co(III) species during the copolymerization. The present study provides a new mechanistic understanding of these binary catalyst systems in which alternating chain-growth and dissociation of propagating carboxylate species derived from the nucleophilic axial anion and the nucleophilic cocatalyst take turns at both sides of the Co(III)-Salen center. This significantly increases the reaction rate and also helps to stabilize the active SalenCo(III) against decomposition to inactive SalenCo(II) even at low CO(2) pressures and/or relatively high temperatures.

Unprecedented enantioselectivity and catalytic activity was observed in the asymmetric copolymerization of CO2 with meso-epoxides (including the less reactive cyclopentene oxide) mediated by the dinuclear Co(III) complex (S,S,S,S)-1 under mild conditions. The resultant copolymers possess more than 99 % carbonate linkages and a perfectly isotactic structure.