Influence of Metal Identity and Complex Nuclearity in Kumada Cross-Coupling Polymerizations with a Pyridine Diimine-Based Ligand Scaffold.
| Autor: | King AJ; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27514, United States., Wang J; Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States., Liu T; Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States., Raghavan A; Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States., Tomson NC; Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States., Zhukhovitskiy AV; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27514, United States. |
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| Jazyk: | angličtina |
| Zdroj: | ACS polymers Au [ACS Polym Au] 2023 Nov 08; Vol. 3 (6), pp. 475-481. Date of Electronic Publication: 2023 Nov 08 (Print Publication: 2023). |
| DOI: | 10.1021/acspolymersau.3c00022 |
| Abstrakt: | Cross-coupling polymerizations have fundamentally changed the field of conjugated polymers (CPs) by expanding the scope of accessible materials. Despite the prevalence of cross-coupling in CP synthesis, almost all polymerizations rely on mononuclear Ni or Pd catalysts. Here, we report a systematic exploration of mono- and dinuclear Fe and Ni precatalysts with a pyridine diimine ligand scaffold for Kumada cross-coupling polymerization of a donor thiophene and an acceptor benzotriazole monomers. We observe that variation of the metal identity from Ni to Fe produces contrasting polymerization mechanisms, while complex nuclearity has a minimal impact on reactivity. Specifically, Fe complexes appear to catalyze step-growth Kumada polymerizations and can readily access both Csp 2 -Csp 3 and Csp 2 -Csp 2 cross-couplings, while Ni complexes catalyze chain-growth polymerizations and predominantly Csp 2 -Csp 2 cross-couplings. Thus, our work sheds light on important design parameters for transition metal complexes used in cross-coupling polymerizations, demonstrates the viability of iron catalysis in Kumada polymerization, and opens the door to novel polymer compositions. Competing Interests: The authors declare no competing financial interest. (© 2023 The Authors. Published by American Chemical Society.) |
| Databáze: | MEDLINE |
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