Dinuclear chromium complexes with [OSSO]-type ligands in the copolymerization of epoxides with CO₂and phthalic anhydride

Abstract

In this study, a new family of dinuclear chromium complexes (1-3) containing bis-thioether-diphenolate ligands has been introduced for the copolymerization of epoxides with carbon dioxide and with phthalic anhydride. Catalyst...

Ring Opening Copolymerization of Epoxides with CO2 and Organic Anhydrides Promoted by Dinuclear [OSSO]‐type Metal Complexes

“…[48,49] In our previous study, we observed similar behaviour in the terpolymerization PO/CO 2 /PA activated by the 1/PPNCl system. [44] This observation reaffirms the high regioselectivity of complex 1 during the terpolymerization reaction. Switching from SA to diglycolic anhydride (DGA) showed improved catalytic activity for 1/PPNCl in the terpolymerization reaction with PO/CO 2 /DGA, even at a lower temperature of 45 °C.…”

“…Terpolymerization of Epoxide/CO 2 /Cyclic Anhydride The [OSSO]-type pro-ligand and the corresponding dinuclear metal complexes 1 and 2 (Scheme 2) were synthesized and fully characterized according to our prior reported work. [43,44] The optimized conditions for terpolymerization of epoxide/carbon dioxide with cyclic anhydride were found for catalyst loading 0.10 mol % and (bis(triphenylphosphine)iminium chloride) (PPNCl, 0.5-1.0 mol), and p CO 2 = 20 bar by following our previous work. [44] In our initial terpolymerization experiment, we reacted propylene oxide (PO) and aliphatic succinic anhydride (SA) in a 10 : 1 molar ratio with carbon dioxide, catalyzed by 1/PPNCl.…”

“…[43,44] The optimized conditions for terpolymerization of epoxide/carbon dioxide with cyclic anhydride were found for catalyst loading 0.10 mol % and (bis(triphenylphosphine)iminium chloride) (PPNCl, 0.5-1.0 mol), and p CO 2 = 20 bar by following our previous work. [44] In our initial terpolymerization experiment, we reacted propylene oxide (PO) and aliphatic succinic anhydride (SA) in a 10 : 1 molar ratio with carbon dioxide, catalyzed by 1/PPNCl. The reaction occurred at 20 bars of CO 2 and a temperature of 45 °C over 24 hours.…”

“…We have recently developed iron and chromium complexes for highly efficient epoxide coupling with CO 2 . [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] In particular, dinuclear [OSSO]-type iron(III) [43] and -chromium(III) [44] complexes (Scheme 2) showed good perform-ances in the ROCOP of epoxides with CO 2 and phthalic anhydride. Here, we report on the use of these systems in the terpolymerization of a wide range of epoxides with CO 2 and organic anhydrides, showing the potential and versatility of these systems for synthesizing new polymeric materials.…”

Synthesis of Mono- and Dinuclear Aluminum Complexes Bearing Aromatic Amino-Phenolato Ligands: A Comparative Study in the Ring-Opening Polymerization of Cyclohexene Oxide

“…In comparison, the order of 2 was similar to the results of some bimetallic complexes, supporting the involvement of two metal centers during the polymerization process. Different reaction orders were also found in the reported iron(III)-alkoxide complexes and chromium complexes, implying that there were probably different reaction pathways for the ROP of CHO initiated by dinuclear complex 2 and mononuclear complex 1 .…”