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The Impact of Charge in a Ni(II) Polymerization Catalyst

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2021

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ACS Catalysis. ACS Publications. 2021, 11(9), pp. 5358-5368. eISSN 2155-5435. Available under: doi: 10.1021/acscatal.1c00778

Zusammenfassung

A direct comparison between neutral active sites and their corresponding cationic analogues is enabled by protonation of neutral bis(imino)phenoxy complexes, active for ethylene polymerization. The additional imine motif compared to parent salicylaldiminato catalysts does not influence the microstructure of the products in ethylene polymerization, but allows for the incorporation of a proton right next to the active center in an N···H+···O bridge yielding cationic complexes. These show an increased Ni–O bond length and a drastically reduced electron density on the Ni atom. In pressure reactor experiments, two different catalysts that produce linear HDPE or undergo extensive chain walking, respectively, in their neutral version, both produce short chain oligomers when the catalyst is charged cationically. A mechanistic analysis by DFT methods reveals an increased propensity for β-hydride elimination compared to ethylene insertion chain growth for the cationic complexes. This results from a higher relative stability of β-agostic species vs olefin-coordinated species.

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540 Chemie

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ethylene polymerization, protonation, neutral catalyst, cationic catalyst, charge, microstructure

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ISO 690SCHIEBEL, Eva, Maria VOCCIA, Laura FALIVENE, Lucia CAPORASO, Stefan MECKING, 2021. The Impact of Charge in a Ni(II) Polymerization Catalyst. In: ACS Catalysis. ACS Publications. 2021, 11(9), pp. 5358-5368. eISSN 2155-5435. Available under: doi: 10.1021/acscatal.1c00778
BibTex
@article{Schiebel2021Impac-53917,
  year={2021},
  doi={10.1021/acscatal.1c00778},
  title={The Impact of Charge in a Ni(II) Polymerization Catalyst},
  number={9},
  volume={11},
  journal={ACS Catalysis},
  pages={5358--5368},
  author={Schiebel, Eva and Voccia, Maria and Falivene, Laura and Caporaso, Lucia and Mecking, Stefan}
}
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