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Issue 30, 2019
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Photolytic, radical-mediated hydrophosphination: a convenient post-polymerisation modification route to P-di(organosubstituted) polyphosphinoboranes [RR′PBH2]n

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Abstract

Polymers with a phosphorus-boron main chain have attracted interest as novel inorganic materials with potentially useful properties since the 1950s. Although examples have recently been shown to be accessible via several routes, the materials reported so far have been limited to P-mono(organosubstituted) materials, [RHPBH2]n, containing P–H groups. Here we report a general route for the post-polymerisation modification of such polyphosphinoboranes giving access to a large range of previously unknown examples featuring P-disubstituted units. Insertion of alkenes, R′CH[double bond, length as m-dash]CH2 into the P–H bonds of poly(phenylphosphinoborane), [PhHPBH2]n was facilitated by irradiation under UV light in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPAP) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under benchtop conditions giving high molar mass, air-stable polymers [PhR′PBH2]n with controlled functionalisation and tunable material properties. The mechanistic explanation for the favourable effect of the addition of TEMPO was also investigated and was proposed to be a consequence of reversible binding to radical species formed from the photolysis of DMPAP. This new methodology was also extended to the formation of crosslinked gels and to water-soluble bottlebrush copolymers showcasing applicability to form a wide range of polyphosphinoborane-based soft materials with tunable properties.

Graphical abstract: Photolytic, radical-mediated hydrophosphination: a convenient post-polymerisation modification route to P-di(organosubstituted) polyphosphinoboranes [RR′PBH2]n

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Publication details

The article was received on 22 Mar 2019, accepted on 05 Jun 2019 and first published on 06 Jun 2019


Article type: Edge Article
DOI: 10.1039/C9SC01428D
Chem. Sci., 2019,10, 7281-7289
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Photolytic, radical-mediated hydrophosphination: a convenient post-polymerisation modification route to P-di(organosubstituted) polyphosphinoboranes [RR′PBH2]n

    A. W. Knights, S. S. Chitnis and I. Manners, Chem. Sci., 2019, 10, 7281
    DOI: 10.1039/C9SC01428D

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