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    Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes

    Access Status
    Fulltext not available
    Authors
    Loong Tan, N.S.
    Nealon, G.L.
    Turner, G.F.
    Moggach, S.A.
    Ogden, Mark
    Massi, Max
    Lowe, Andrew
    Date
    2020
    Type
    Journal Article
    
    Metadata
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    Citation
    Loong Tan, N.S. and Nealon, G.L. and Turner, G.F. and Moggach, S.A. and Ogden, M.I. and Massi, M. and Lowe, A.B. 2020. Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes. ACS Macro Letters. 9 (1): pp. 56-60.
    Source Title
    ACS Macro Letters
    DOI
    10.1021/acsmacrolett.9b00975
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    URI
    http://hdl.handle.net/20.500.11937/77877
    Collection
    • Curtin Research Publications
    Abstract

    The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography.

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