Polyphosphinoborane Block Copolymer Synthesis Using Catalytic Reversible Chain-Transfer Dehydropolymerization

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

doi:10.1002/anie.202216106

Polyphosphinoborane Block Copolymer Synthesis Using Catalytic Reversible Chain-Transfer Dehydropolymerization

Angew Chem Int Ed Engl. 2023 Jan 16;62(3):e202216106. doi: 10.1002/anie.202216106. Epub 2022 Dec 8.

Authors

James J Race^{1

2}, Alex Heyam¹, Matthew A Wiebe³, J Diego-Garcia Hernandez³, Charlotte E Ellis³, Shixing Lei³, Ian Manners^{3

4}, Andrew S Weller¹

Affiliations

¹ Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
² Chemistry Research Laboratories, University of Oxford, Oxford, OX1 3TA, UK.
³ Department of Chemistry, University of Victoria, Victoria, BC, V8P 5C2, Canada.
⁴ Centre for Advanced Materials and Related Technology (CAMTEC), University of Victoria, Victoria, BC, V8P 5C2, Canada.

Abstract

An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism-led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H₃ B ⋅ PRH₂ (R=Ph, n-hexyl), using the simple pre-catalyst [Rh(Ph₂ PCH₂ CH₂ PPh₂ )₂ ]Cl. Speciation, mechanism and polymer chain growth studies support a step-growth process where reversible chain transfer occurs, i.e. H₃ B ⋅ PRH₂ /oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H₂ BPPhH]₁₁₀ -b-[H₂ BP(n-hexyl)H]₁₁ can be synthesized and self-assembles in solution to form either rod-like micelles or vesicles depending on solvent polarity.

Keywords: Block Copolymer; Borane; Dehydropolymerization; Phosphine; Self-Assembly.

Abstract

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