Polyphosphinoborane block copolymer synthesis using catalytic reversible chain-transfer dehydropolymerization




Race, James J.
Heyam, Alex
Wiebe, Matthew A.
Hernandez, J. Diego-Garcia
Ellis, Charlotte E.
Lei, Shixing
Manners, Ian
Weller, Andrew S.

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Angewandte Chemie International Edition


An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism-led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H₃B ⋅ PRH₂ (R=Ph, n-hexyl), using the simple pre-catalyst [Rh(Ph₂PCH₂CH₂PPh₂)₂]Cl. Speciation, mechanism and polymer chain growth studies support a step-growth process where reversible chain transfer occurs, i.e. H₃B ⋅ PRH₂/oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H₂BPPhH]₁₁₀-𝑏-[H₂BP(n-hexyl)H]₁₁ can be synthesized and self-assembles in solution to form either rod-like micelles or vesicles depending on solvent polarity.




Race, J. J., Heyam, A., Wiebe, M. A., Hernandez, J. D-G., Ellis, C. E., Lei, S., Manners, I., & Weller, A. S. (2023). Polyphosphinoborane block copolymer synthesis using catalytic reversible chain‐transfer dehydropolymerization. Angewandte Chemie International Edition, 62(3). https://doi.org/10.1002/anie.202216106