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Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis

Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis

Type of Publication: Journal article
Publication status: Published
Author: Kenyon, Philip; Falivene, Laura; Caporaso, Lucia; Mecking, Stefan
Year of publication: 2019
Published in: ACS Catalysis ; 9 (2019), 12. - pp. 11552-11556. - eISSN 2155-5435
DOI (citable link): https://dx.doi.org/10.1021/acscatal.9b04028
Summary:
The influence of the labile ligand on the rate of β-hydride elimination (BHE) for salicylaldiminato Ni(II) complexes is shown using a series of precatalysts which differ only in the labile ligand but produce polyethylenes with a range of molecular weights (Mn = 466 to 100 kg mol–1), degrees of branching (1.7 to 7.3 branches/1000 C), and melting temperatures (from 132 to 123 °C) under the same conditions. The use of a weakly coordinating solvent (diethyl ether) was able to suppress this increase in BHE. DFT studies on a related salicylaldiminato Ni(II) complex show that BHE can feasibly occur following recombination of the labile ligand with the catalyst.
Subject (DDC): 540 Chemistry
Keywords: homogeneous nickel(II) catalysts, ethylene insertion polymerization, mechanism, density functional theory, polyethylene
Bibliography of Konstanz: Yes
Refereed: No

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KENYON, Philip, Laura FALIVENE, Lucia CAPORASO, Stefan MECKING, 2019. Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis. In: ACS Catalysis. 9(12), pp. 11552-11556. eISSN 2155-5435. Available under: doi: 10.1021/acscatal.9b04028

@article{Kenyon2019-12-06Ancil-47759, title={Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis}, year={2019}, doi={10.1021/acscatal.9b04028}, number={12}, volume={9}, journal={ACS Catalysis}, pages={11552--11556}, author={Kenyon, Philip and Falivene, Laura and Caporaso, Lucia and Mecking, Stefan} }

2019-12-06 Mecking, Stefan Caporaso, Lucia 2019-12-02T10:31:37Z Falivene, Laura Mecking, Stefan Kenyon, Philip 2019-12-02T10:31:37Z Caporaso, Lucia eng Falivene, Laura The influence of the labile ligand on the rate of β-hydride elimination (BHE) for salicylaldiminato Ni(II) complexes is shown using a series of precatalysts which differ only in the labile ligand but produce polyethylenes with a range of molecular weights (M<sub>n</sub> = 466 to 100 kg mol<sup>–1</sup>), degrees of branching (1.7 to 7.3 branches/1000 C), and melting temperatures (from 132 to 123 °C) under the same conditions. The use of a weakly coordinating solvent (diethyl ether) was able to suppress this increase in BHE. DFT studies on a related salicylaldiminato Ni(II) complex show that BHE can feasibly occur following recombination of the labile ligand with the catalyst. Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis Kenyon, Philip

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