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    Mechanism of Insertion Polymerization of Allyl Ethers

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    Type
    Article
    Authors
    Wimmer, Florian P.
    Caporaso, Lucia
    Cavallo, Luigi cc
    Mecking, Stefan
    Falivene, Laura cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2018-06-07
    Online Publication Date
    2018-06-07
    Print Publication Date
    2018-06-26
    Permanent link to this record
    http://hdl.handle.net/10754/630494
    
    Metadata
    Show full item record
    Abstract
    The copolymerization of ethylene (E) with allyl ethyl ether (AEE) by [di(2-dianisyl)phosphine-2-yl]benzenesulfonato Pd(II) as a catalyst is investigated by DFT calculations and compared with the copolymerization of E with diallyl ether (DAE). For AEE, both 1,2- and 2,1-monomer insertions lead to a very stable O-Chelate product (a five-membered and a four-membered ring, respectively) that hinders any further ethylene insertion. As for DAE, a first 2,1-insertion (favored by 1.8 kcal mol vs the 1,2-insertion) leads to the four-membered O-Chelate product that easily evolves to the most stable intermediate with the second DAE C=C bond coordinated to the metal promoting the following 1,2-insertion. The 2,1 + 1,2 DAE insertion product, bearing a five-membered cyclic unit, is stabilized by a β-agostic interaction that easily opens in favor of E coordination and insertion. Based on the proposed copolymerization mechanism, the stereochemistry of the E/DAE copolymer is studied and the experimental microstructure explained. Finally, [di(2-anisyl)phosphine-2-yl]benzenesulfon(methyl)amido Pd(II) species showing a greater regioselectivity toward a first DAE 2,1-insertion (Δ ΔG of -3.6 kcal mol) are suggested to be a promising catalyst.
    Citation
    Wimmer FP, Caporaso L, Cavallo L, Mecking S, Falivene L (2018) Mechanism of Insertion Polymerization of Allyl Ethers. Macromolecules 51: 4525–4531. Available: http://dx.doi.org/10.1021/acs.macromol.8b00783.
    Sponsors
    F.P.W. thanks the KAUST visiting student research program for funding of his internship at KAUST. Support by the DFG (Me 1388/10-2) is gratefully acknowledged.
    Publisher
    American Chemical Society (ACS)
    Journal
    Macromolecules
    DOI
    10.1021/acs.macromol.8b00783
    Additional Links
    https://pubs.acs.org/doi/10.1021/acs.macromol.8b00783
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.macromol.8b00783
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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