Theoretical Investigation on the Catalytic Activity of Bis-boron Phosphonium Salt for the Copolymerization of Propylene Oxide and Carbon Dioxide

doi:10.1007/s40242-025-5134-5

Abstract

Abstract: This study theoretically investigated the regulation mechanism of catalytic activity in the copolymerization of propylene oxide (PO) and carbon dioxide (CO₂) catalyzed by a well-designed bis-boron phosphonium salt (PBB) catalyst through density functional theory (DFT) calculations. Mechanistic analysis suggests that the alternating copolymerization of PO and CO₂ is thermodynamically and kinetically favorable. The results revealed that initiation efficiency is dependent on the counter anions of phosphonium salt, where Br^- exhibited a higher ring-opening reactivity of PO than Cl^-. The electronic effect of the catalyst for the initiation step is investigated by altering substituent groups in PBB catalysts and the results suggest that the catalytic activity is improved by the substitution of electron-donating groups. On the other hand, the catalytic activity of such PBB catalysts is also significantly dependent on the number of methylene groups (chain length) between the phosphorus center and boron atom, suggesting a synergism and confinement characteristic of PBB catalysts. Interestingly, computational results clearly show that secondary (electrostatic) interaction induced by the tetra-coordinated boron-ate complex stabilizes the transition states of ring-opening of PO and accelerates the polymerization. This work provides theoretical insights for designing efficient supramolecular catalysts and optimizing CO₂ utilization strategies.

Key words: Bis-boron catalyst, Ring-opening reaction, Catalytic activity, Copolymerization, Density functional theory

SONG Xinyuan, ZHOU Haiping, YOU Xiaoxia, WANG Xiaowu, ZHONG Ronglin, SU Zhongmin. Theoretical Investigation on the Catalytic Activity of Bis-boron Phosphonium Salt for the Copolymerization of Propylene Oxide and Carbon Dioxide[J]. Chemical Research in Chinese Universities, 2025, 41(5): 1193-1200.

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