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Anion-binding catalysis enables living cationic polymerization

Nature Synthesis volume 1, pages 815–823 (2022)Cite this article

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Abstract

Anion-binding interactions in nature have enabled the development of organocatalytic transformations; however, even though ionic species act as intermediates or precursors in many polymerizations, these interactions are underappreciated in polymerization catalysis. Here we introduce a powerful anion-binding catalytic strategy for cationic polymerization. In our approach, selenocyclodiphosph(V)azanes were designed as bench-stable hydrogen-bond donors to reversibly activate dormant covalent bonds (C–X, X=Cl, carboxylate and phosphate), in turn to precisely control the equilibrium between dormant covalent precursors and active cationic species under mild conditions. Experimental and computational analysis of this catalytic system revealed the key role of non-covalent anion-binding interactions between the catalyst and substrates. The living and controlled nature of this strategy, coupled with its capability for recycling catalysts and addressing certain fundamental constraints, such as metal residue and rigorous reaction conditions, delivers a versatile and robust living cationic polymerization methodology for precision polymer synthesis.

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Fig. 1: Anion-binding catalysis enables LCP.
Fig. 2: LCP of electron-rich vinyl monomers mediated by anion-binding catalyst 5a.
Fig. 3: NMR spectroscopy titration and low-temperature NMR spectroscopy experiments.
Fig. 4: DFT calculations to simulate the chain initiation and propagation processes.
Fig. 5: Mechanism of anion-binding catalysis for LCP.

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Data availability

All data that support the findings of this study are available within the article and its Supplementary Information. Crystallographic data for the structures in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition nos. 2125756 (5a·CH3CN) and 2142031 (5a·TEACl). Copies of the data can be obtained free of charge from www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant U21A2089, Y.T., and grant 22001243, M.L.) and the Jilin Science and Technology Bureau (Grant 20210402066GH, M.L.). We thank X. Zhang for helpful discussions with the theoretical calculations. We thank the Molecular Scale Lab at Shenzhen University for the MALDI–TOF MS characterization.

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Authors and Affiliations

  1. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, People’s Republic of China

    Maosheng Li, Zhen Zhang, Yan Yan, Wenxiu Lv, Xianhong Wang & Youhua Tao

  2. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, People’s Republic of China

    Zhikai Li

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Contributions

M.L. and Y.T. developed the concept, and co-wrote the manuscript. M.L. and Y.T. designed the experiments, and analysed the results. M.L., Z.Z., Y.Y. and W.L. performed the experiments. Z.L. performed the MALDI–TOF MS experiments. M.L. performed the DFT calculations. Y.T. and X.W. directed the project.

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Correspondence to Youhua Tao.

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Nature Synthesis thanks Frank Leibfarth and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–49, Tables 1–4, materials, experimental procedures, product characterization, computational methodology and supplementary discussion.

Supplementary Data 1

Crystallographic data for compound 5a, CCDC 2125756.

Supplementary Data 2

Crystallographic data for compound 5a•TEACl, CCDC 2142031.

Supplementary Data 3

DFT computational data in .log files for all the transition states and intermediates.

Source data

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Statistical Source Data.

Source Data Fig. 3

Statistical Source Data.

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Statistical Source Data.

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Li, M., Zhang, Z., Yan, Y. et al. Anion-binding catalysis enables living cationic polymerization. Nat. Synth 1, 815–823 (2022). https://doi.org/10.1038/s44160-022-00142-0

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