Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis
KAUST DepartmentKAUST Catalysis Center (KCC)
Online Publication Date2019-11-18
Print Publication Date2019-12-06
Embargo End Date2020-11-18
Permanent link to this recordhttp://hdl.handle.net/10754/660544
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AbstractThe 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.
CitationKenyon, P., Falivene, L., Caporaso, L., & Mecking, S. (2019). Ancillary Ligands Impact Branching Microstructure in Late-Transition-Metal Polymerization Catalysis. ACS Catalysis, 9(12), 11552–11556. doi:10.1021/acscatal.9b04028
SponsorsWe thank Lars Bolk for DSC and GPC analyses. Financial support by SABIC is gratefully acknowledged.
PublisherAmerican Chemical Society (ACS)