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A robust nickel catalyst with an unsymmetrical propyl-bridged diphosphine ligand for catalyst-transfer polymerization

Polymer Journal volume 52, pages 83–92 (2020)Cite this article

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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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  1. Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213-2617, USA

    Matthew A. Baker, Josué Ayuso-Carrillo, Martin R. M. Koos, Anthony J. Varni, Roberto R. Gil & Kevin J. T. Noonan

  2. Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY, 14853-1301, USA

    Samantha N. MacMillan

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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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