Abstract
A new nickel diphosphine catalyst has been synthesized in which the bidentate ligand has two different phosphine donors, a typical PPh2 group and a stronger σ-donating PEt2 group. The catalyst was highly effective for the chain-growth polymerization of a 3-alkylthiophene monomer using a Suzuki–Miyaura cross-coupling. The catalyst is particularly effective for this polymerization in the presence of excess free ligand. The unsymmetrical diphosphine nickel complex reported here represents a new approach to tuning metal-ligand reactivity in the chain-growth polymerization of aromatic monomers. In addition, this new nickel catalyst exhibited increased hydrolytic resistance in the polymerization as compared to commercially available 1,3-bis(diphenylphosphino)propane nickel dichloride.
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Acknowledgements
K.J.T.N. is grateful to the NSF for a CAREER Award (CHE-1455136). The NMR instrumentation at Carnegie Mellon University is partially supported by the NSF (CHE-0130903, CHE-1039870, and CHE-1726525). The authors would also like to thank both Prof. Tsutomu Yokozawa and Prof. Anne McNeil for helpful discussions.
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Baker, M.A., Ayuso-Carrillo, J., Koos, M.R.M. et al. A robust nickel catalyst with an unsymmetrical propyl-bridged diphosphine ligand for catalyst-transfer polymerization. Polym J 52, 83–92 (2020). https://doi.org/10.1038/s41428-019-0259-3
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DOI: https://doi.org/10.1038/s41428-019-0259-3
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