2026-09-20T13:00:37Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/132467 2026-02-20 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

application/pdf en text Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2026-02-19 without embargo terms The student, Alfons Pineda-Knauseder, accepted the attached license on 2025-09-23 at 21:50. The student, Alfons Pineda-Knauseder, submitted this Dissertation for approval on 2025-09-23 at 22:04. This Dissertation was approved for publication on 2025-10-03 at 11:29. DSpace SAF Submission Ingestion Package generated from Vireo submission #22812 on 2026-02-19 at 18:24:19 Towards polyethylene-based materials with non-alternatively incorporated carbon monoxide monomer Pineda-Knauseder, Alfons Jose 2025-10-03 Guironnet, Damien S. Guironnet, Damien S. Mirica, Liviu M. Olshansky, Lisa Snyder, Benjamin E.R. organometallics catalysis polyketone nickel palladium coordination polymerization polymerization copolymerization ethylene/carbon monoxide copolymer eng The synthesis of ethylene/carbon monoxide copolymers (polyketones) was pursued via insertion polymerization methods through palladium(II) and nickel(II) catalysis. Specifically, phosphine sulfonate palladium(II) precatalysts derived from the in situ complexation of palladium(II) acetate and phosphine sulfonate, were found to facilitate the copolymerization of ethylene and carbon monoxide, typically yielding polyketones with a CO composition ranging from 40 – 50 mol%. Well-defined (phosphine sulfonate)Pd(II)Me precatalysts, on the other hand, typically resulted in nearly alternating (~ 50 mol% CO) polyketones. Alternatives synthetic routes toward polyketones via the ring-opening metathesis copolymerization (ROMP) of 3-cyclopentanone with 1,5-cyclooctadiene followed by olefin hydrogenation were also pursued. Five new κ2-[phosphine-(di)phenolate]Ni(II)Me complexes with either mono- or trinuclear structures were also synthesized, characterized, and utilized in the catalytic (co)polymerization of ethylene. These complexes were accessed from the complexation of (TMEDA)NiMe2 (N,N,N′,N′-tetramethylethylenediamine nickel(II) dimethyl) with either a BINOL (1,1′-bi-2-naphthol)-based phosphine diphenol (P,O) ligand or an analogous ligand which features an ethyl ether in place of the nonortho phenol. All complexes were active for ethylene homopolymerization (featuring activity up to 81.3 × 105 g polymer × mol Ni–1 × hr–1 and Mn up to 4.2 kg/mol) and ethylene/methyl acrylate (MA) copolymerization (MAmol % up to 8.3%). Moreover, three of the five complexes were shown to be active for ethylene/carbon monoxide copolymerization, yielding up to 4.8 mol% CO copolymers. 2025-12 Thesis https://hdl.handle.net/2142/132467 Copyright 2025 Alfons Pineda-Knauseder Chemistry Chemistry University of Illinois Urbana-Champaign Ph.D. Dissertation