| Title |
Dinuclear chromium complexes with [OSSO]-type ligands in the copolymerization of epoxides with CO2 and phthalic anhydride |
| ID_Doc |
18610 |
| Authors |
Niknam, F; Denk, A; Buonerba, A; Rieger, B; Grassi, A; Capacchione, C |
| Title |
Dinuclear chromium complexes with [OSSO]-type ligands in the copolymerization of epoxides with CO2 and phthalic anhydride |
| Year |
2023 |
| Published |
Catalysis Science & Technology, 13.0, 16 |
| DOI |
10.1039/d3cy00832k |
| Abstract |
In this study, a new family of dinuclear chromium complexes (1-3) containing bis-thioether-diphenolate ligands has been introduced for the binary copolymerization of carbon dioxide and epoxides and ternary copolymerization of the latter with phthalic anhydride. Complex 1 (0.1 mol%) in combination with (bis(triphenylphosphine)iminium chloride) (PPNCl, 0.5 mol) at 45 & DEG;C and 20 bar of CO2 showed high regioselective copolymerization to polypropylene carbonate (PPC) with conversion (up to 91%) and selectivity (up to 95%). The data presented in this work have consistently shown that complex 1 displayed higher catalytic activity in copolymerizing epoxides with CO2 than complexes 2, 3, and the analogous mononuclear 4. At the same time, complex 1 showed good catalytic properties in the terpolymerization of epoxides/CO2/phthalic anhydride among the tested complexes 2 and 4. In the case of cyclohexene oxide and vinylcyclohexene oxide, a selectivity of more than 99% towards polycyclohexene carbonate (PCHC) and polyvinylcyclohexene carbonate (PVCHC) with a TOF as high as 41 h(-1) in the poly(ester-block-carbonate) was observed. Notably, a conversion higher than 99% towards the polyester block was also observed for all the studied epoxides. A bimetallic intramolecular cooperative mechanism was proposed for the copolymerization of propylene oxide and CO2 based on the first-order dependence with respect to complex 1 by the kinetic investigations. |
| Author Keywords |
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| Index Keywords |
Index Keywords |
| Document Type |
Other |
| Open Access |
Open Access |
| Source |
Science Citation Index Expanded (SCI-EXPANDED) |
| EID |
WOS:001031630000001 |
| WoS Category |
Chemistry, Physical |
| Research Area |
Chemistry |
| PDF |
https://pubs.rsc.org/en/content/articlepdf/2023/cy/d3cy00832k
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