Dynamic Coordination Enables Moisture-Tolerant Organoaluminum Catalysis for Controlled Ring-Opening Polymerization
5 affiliations
- 1State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology; Shandong Key Laboratory of Advanced Organosilicon Materials and Technologies; College of Polymer Science and Engineering
- 2Qingdao University of Science and Technology
- 3College of Chemical Engineering
- 4College of Material Science and Engineering
- 5State Key Laboratory of Chemical Engineering and Low-carbon Technology, College of Chemical and Biological Engineering, Zhejiang University, 866 Yuhangtang Road, Hangzhou, Zhejiang, China, 310058
Abstract
Reconciling high catalytic activity with air/moisture stability remains a fundamental challenge in the development of efficient organometallic catalysts for the ring‑opening polymerization (ROP). In this contribution, we present a dynamic Lewis-base coordination strategy that regulates the coordination environment of an organoaluminum catalyst to balance these competing requirements. A structurally simple organoaluminum catalyst featuring a dynamic THF ligand, MeAl(BHT)2(THF) (BHT = 2,6-di-tert-butyl-4-methylphenoxy), is easily prepared from commercially available trimethylaluminum, 2,6-di-tert-butyl-4-methylphenol and tetrahydrofuran (THF) without tedious purification. In contrast to the parent MeAl(BHT)2, MeAl(BHT)2(THF) exhibits substantially enhanced air/moisture tolerance while retaining good catalytic activity and controllability toward the ROP of a diversity of lactones and lactide. Notably, MeAl(BHT)2(THF) enable controlled ROP of commercially as-received monomers without prior drying or purification. In particular, MeAl(BHT)2(THF) achieves a high turnover frequency (TOF) of 8400 h-1 for the bulk ROP of l-lactide conducted at 180 °C in air. The single-crystal structural analysis and in-situ NMR experiments collaboratively confirm the dynamic coordination and dissociation of the THF ligand, which accounts for the balance of high activity and moisture tolerance. This dynamic ligand strategy affords a robust organometallic catalyst with facile preparation, good activity and ambient stability, facilitating practical scalable aliphatic polyester synthesis.
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BibTeX
@misc{yan2026dynamic,
title = {{Dynamic Coordination Enables Moisture-Tolerant Organoaluminum Catalysis for Controlled Ring-Opening Polymerization}},
author = {Qin Yan and Pingtao Ge and Shuyi Wang and Yong Shen and Zhibo Li},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009113/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009113/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Dynamic Coordination Enables Moisture-Tolerant Organoaluminum Catalysis for Controlled Ring-Opening Polymerization
AU - Qin Yan
AU - Pingtao Ge
AU - Shuyi Wang
AU - Yong Shen
AU - Zhibo Li
PY - 2026
DA - 2026/09/20
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009113/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009113/v1
AB - Reconciling high catalytic activity with air/moisture stability remains a fundamental challenge in the development of efficient organometallic catalysts for the ring‑opening polymerization (ROP). In this contribution, we present a dynamic Lewis-base coordination strategy that regulates the coordination environment of an organoaluminum catalyst to balance these competing requirements. A structurally simple organoaluminum catalyst featuring a dynamic THF ligand, MeAl(BHT)2(THF) (BHT = 2,6-di-tert-butyl-4-methylphenoxy), is easily prepared from commercially available trimethylaluminum, 2,6-di-tert-butyl-4-methylphenol and tetrahydrofuran (THF) without tedious purification. In contrast to the parent MeAl(BHT)2, MeAl(BHT)2(THF) exhibits substantially enhanced air/moisture tolerance while retaining good catalytic activity and controllability toward the ROP of a diversity of lactones and lactide. Notably, MeAl(BHT)2(THF) enable controlled ROP of commercially as-received monomers without prior drying or purification. In particular, MeAl(BHT)2(THF) achieves a high turnover frequency (TOF) of 8400 h-1 for the bulk ROP of l-lactide conducted at 180 °C in air. The single-crystal structural analysis and in-situ NMR experiments collaboratively confirm the dynamic coordination and dissociation of the THF ligand, which accounts for the balance of high activity and moisture tolerance. This dynamic ligand strategy affords a robust organometallic catalyst with facile preparation, good activity and ambient stability, facilitating practical scalable aliphatic polyester synthesis.
ER -