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Statistical Analysis of Catalytic Performance in Ethylene/Methyl Acrylate Copolymerization Using Palladium/Phosphine-Sulfonate Catalysts
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    Statistical Analysis of Catalytic Performance in Ethylene/Methyl Acrylate Copolymerization Using Palladium/Phosphine-Sulfonate Catalysts
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    • Shumpei Akita
      Shumpei Akita
      Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    • Jing-Yao Guo
      Jing-Yao Guo
      Department of Chemistry, College of Science, The University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
      More by Jing-Yao Guo
    • Falk W. Seidel
      Falk W. Seidel
      Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    • Matthew S. Sigman*
      Matthew S. Sigman
      Department of Chemistry, College of Science, The University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States
      *Email: [email protected] (M.S.S.).
    • Kyoko Nozaki*
      Kyoko Nozaki
      Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
      *Email: [email protected] (K.N.).
      More by Kyoko Nozaki
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    Organometallics

    Cite this: Organometallics 2022, 41, 22, 3185–3196
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    https://doi.org/10.1021/acs.organomet.2c00066
    Published March 29, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    For various types of palladium complexes bearing phosphine-sulfonate (PS) ligands used in the coordination–insertion copolymerization of olefins with polar monomers, characteristic features of the ligands, such as electronic and steric properties, have been discussed to describe their catalytic performance. Aiming at further analysis of the literature data, here we report the development of a statistical method for how the ligand impacts the performance of a Pd-catalyzed copolymerization of ethylene and methyl acrylate (MA). During our investigation, ligand features important for the resultant molecular weight of the obtained polymers were identified. Consistent with previously suggested important parameters, the electron density on the palladium center and maximum width of the substituents on the phosphorus atom (B5) were found to be significant for catalyst performance. We also found that additional features impact reaction outputs. As an example, the lower occupancy of the palladium dz2 orbital results in an increase of molecular weight and catalyst activity in both ethylene homopolymerization and ethylene/methyl acrylate copolymerization. Furthermore, it was predicted that a larger bite angle of the ligand increased the activity of ethylene/methyl acrylate copolymerization without impacting the molecular weight. On the basis of these machine learning predictions, three thiophene derived PS-type catalysts were synthesized and tested for MA/ethylene copolymerization. Unexpectedly, rather than the one predicted to enhance catalytic performance, a synthetic intermediate to this ligand exhibited higher activity albeit with the expense of molecular weight and MA incorporation. The inconsistency between the prediction and the experimental result is likely a result of insufficient training data for the catalyst with a different linker moiety. However, the unexpected finding that chlorination of the ligand backbone increases the overall catalyst performance will inspire an avenue for PS catalyst development.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.2c00066.

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    CCDC 21093172109318 and 2109322 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.; fax: +44 1223 336033.

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    This article is cited by 8 publications.

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    Organometallics

    Cite this: Organometallics 2022, 41, 22, 3185–3196
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.2c00066
    Published March 29, 2022
    Copyright © 2022 American Chemical Society

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