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Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates

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  • Zheng-Lin Wang

    (Peking University)

  • Rong Zhu

    (Peking University)

Abstract

In contrast to allyl palladium complexes, propargylic/allenylic palladium species display complex reactivities that limit their implementation in polymer chemistry, especially for chain-growth polymerizations. Here we report an example of controlled chain-growth polymerization via propargyl/allenyl palladium intermediates. Vinylidenecyclopropane 1,1-dicarboxylate (VDCP), a unique allenylic electrophile, selectively reacts via the σ-allenyl palladium complex rather than the more common π-propargyl pathway, thereby unlocking a chain-growth process. Based on this concept, precise synthesis of alkyne-backbone polymers is realized, featuring fast rate, high molecular weight, narrow dispersity, high chemoselectivity, and excellent end-group fidelity. We demonstrate preparation of unsaturated macromolecules with advanced sequences and architectures using this method, including block, gradient, and graft copolymers.

Suggested Citation

  • Zheng-Lin Wang & Rong Zhu, 2025. "Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates," Nature Communications, Nature, vol. 16(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57723-8
    DOI: 10.1038/s41467-025-57723-8
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