Synthesis, Characterization, and Properties of Poly(aryl)phosphinoboranes Formed via Iron‐Catalyzed Dehydropolymerization

The dehydropolymerization of the primary phosphine–boranes, RPH2•BH3 (1a–f) (R = 3,4‐(OCH2O)C6H3 (a), Ph (b), p‐(CF3O)C6H4 (c), 3,5‐(CF3)2C6H3 (d), 2,4,6‐(CH3)3C6H2 (e), 2,4,6‐tBu3C6H2 (f)) is explored using the precatalyst [CpFe(CO)2OTf] (I) (OTf = OS(O)2CF3), based on the earth abundant element Fe...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 2017-10, Vol.218 (19), p.n/a
Main Authors: Turner, Joshua R., Resendiz‐Lara, Diego A., Jurca, Titel, Schäfer, André, Vance, James R., Beckett, Laura, Whittell, George R., Musgrave, Rebecca A., Sparkes, Hazel A., Manners, Ian
Format: Article
Language:English
Subjects:
Aromatic compounds
Boranes
catalysis
Chemical synthesis
crystal structure
heteroatom‐containing polymers
Ionization
Ions
Iron
Liquid chromatography
Mass spectrometry
NMR spectroscopy
Polydispersity
Polyelectrolytes
polymerization
Surface properties
Surface stability
synthesis
Thermal stability
Thin films
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Summary:The dehydropolymerization of the primary phosphine–boranes, RPH2•BH3 (1a–f) (R = 3,4‐(OCH2O)C6H3 (a), Ph (b), p‐(CF3O)C6H4 (c), 3,5‐(CF3)2C6H3 (d), 2,4,6‐(CH3)3C6H2 (e), 2,4,6‐tBu3C6H2 (f)) is explored using the precatalyst [CpFe(CO)2OTf] (I) (OTf = OS(O)2CF3), based on the earth abundant element Fe. Formation of polyphosphinoboranes [RPH‐BH2]n (2a–e) is confirmed by multinuclear NMR spectroscopy, but no conversion of 1f to 2f is detected. Analysis by electrospray ionization mass spectrometry confirms the presence of the anticipated polymer repeat units for 2a–e. Gel permeation chromatography (GPC) confirms the polymeric nature of 2a–e and indicates number‐average molecular weights (Mn) of 12 000–209 000 Da and polydispersity indices between 1.14 and 2.17. By contrast, thermal dehydropolymerization of 1a–e in the absence of added precatalyst leads to formation of oligomeric material. Interestingly, polyphosphinoboranes 2c and 2d display GPC behavior typical of polyelectrolytes, with a hydrodynamic radius dependent on concentration. The thermal transition behavior, thermal stability, and surface properties of thin films are also studied. Dehydropolymerization of primary phosphine–boranes by a homogenous catalyst based on Fe is presented. A range of high‐molecular‐weight primary polyphosphinoboranes is characterized and their properties are delineated. Furthermore, thermal analysis, contact angle, and soft lithography studies are carried out.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.201700120