Issue 31, 2023

Cationic tetranuclear macrocyclic CaCo3 complexes as highly active catalysts for alternating copolymerization of propylene oxide and carbon dioxide

Abstract

We found that a cationic hetero tetranuclear complex including a calcium and three cobalts exhibited high catalytic activity toward alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO2). The tertiary anilinium salt [PhNMe2H][B(C6F5)4] was the best additive to generate the cationic species while maintaining polymer selectivity and carbonate linkage, even under 1.0 MPa CO2. Density functional theory calculations clarified that the reaction pathway mediated by the cationic complex is more favorable than that mediated by the neutral complex by 1.0 kcal mol−1. We further found that the flexible ligand exchange between Ca and Co ions is important for the alternating copolymerization to proceed smoothly.

Graphical abstract: Cationic tetranuclear macrocyclic CaCo3 complexes as highly active catalysts for alternating copolymerization of propylene oxide and carbon dioxide

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Febr. 2023
Accepted
11 Jūl. 2023
First published
12 Jūl. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 8262-8268

Cationic tetranuclear macrocyclic CaCo3 complexes as highly active catalysts for alternating copolymerization of propylene oxide and carbon dioxide

H. Nagae, S. Matsushiro, J. Okuda and K. Mashima, Chem. Sci., 2023, 14, 8262 DOI: 10.1039/D3SC00974B

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