Chromium-Catalyzed CO₂–Epoxide Copolymerization

Abstract

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En route to CO2-containing renewable materials: catalytic synthesis of polycarbonates and non-isocyanate polyhydroxyurethanes derived from cyclic carbonates

“…91,92 Alternatively, when no ionic part is present in the metal-catalyst, a co-catalyst Table 2). Several metal complexes have been successfully applied for this reaction including Co, 74,93 Zn, 94 Al 64 and Cr, 95,96 and examples of Fe 97 and In 98 complexes have also been reported (see Fig. 3, structures 7-10 as examples).…”

Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by chromium complexes bearing semirigid [ONSO]-type ligands

“…(c), (e), (b), (c), Prominently employed are the [ONNO]‐type tetradentate dianionic ligands with Cr III and Co III centers as they provide remarkable activity for CO 2 /epoxide copolymerization . But upon screening all homogeneous metal catalysts to date, very few examples of ligands bearing soft Lewis base donors are found for this copolymerization process . Recently, Duchateau and coworkers employed an aminophosphine chelate on a Cr III complex to catalyze the production of poly(cyclohexene carbonate) (PCHC) from CO 2 and cyclohexene oxide (CHO).…”

“…Recently, Duchateau and coworkers employed an aminophosphine chelate on a Cr III complex to catalyze the production of poly(cyclohexene carbonate) (PCHC) from CO 2 and cyclohexene oxide (CHO). The catalyst, however, showed low activity (turnover frequency (TOF) < 30 h −1 ) and provided low molecular weight polymers ( M n < 1800 Da) containing detectable ether linkages (≥6%) . (a) Capacchione and coworkers introduced a dinuclear Fe III complex coordinated by a dithioether–triphenolate ligand for the coupling reaction of CO 2 with epoxides, but this complex produces cyclic carbonates exclusively .…”

Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides

“…After these first reports, many mononuclear and dinuclear chromium Salen complexes have been developed for the copolymerization of epoxides with CO2 allowing the synthesis, with high activity, of new copolymer microstructures ( Figure 6) [56,57]. In the search of alternative ligands for the CO2/epoxide chemistry, the first example of chromium catalysts bearing a soft donor atom in the ligand skeleton was reported by Duchateau and coworkers only in 2014 and regarded the utilization of two chromium(III) complexes having an aminophosphine bidentate ligand ( Figure 7) [58]. These catalysts showed moderate catalytic activity in the copolymerization of CO2 with CHO affording low molecular weight PCHC (Mn up to 1930 g mol −1 ).…”

“…Chromium(III)-Aminophosphine complexes developed by Duchateau for the coupling of CO 2 with CHO[58].In this field, the choice of sulfur as the soft Lewis base is even more recent. In 2015, the tetradentate [OSSO]-type chromium complexes (1-4) were developed by Liu and coworkers for the copolymerization of various epoxides with phthalic anhydride and subsequently used for the copolymerization of CO 2 with vinylcyclohexeneoxide (VCHO) (Figure 8)[59].Catalysts 2020, 10, x FOR PEER REVIEW 6 of 20…”