Work

Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates

Year: 2025

Type: article

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. In contrast to allyl palladium complexes, propargylic/allenylic palladium species display complex reactivities that limit their implementation in polymer chemistry. Here, the authors report an example of controlled chain-growth polymerization via propargyl/allenyl palladium intermediates.

Source: Nature Communications

DOI: 10.1038/s41467-025-57723-8

Authors: Zheng-Lin Wang, Rong Zhu

Institutions: Peking University, Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering, Ministry of Education

Language: English

Topic: Advanced Polymer Synthesis and Characterization

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,990

Funders: National Natural Science Foundation of China, Natural Science Foundation of Beijing Municipality