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Catalytic living ring-opening metathesis polymerization

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A Retraction to this article was published on 11 April 2018

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Abstract

In living ring-opening metathesis polymerization (ROMP), a transition-metal–carbene complex polymerizes ring-strained olefins with very good control of the molecular weight of the resulting polymers. Because one molecule of the initiator is required for each polymer chain, however, this type of polymerization is expensive for widespread use. We have now designed a chain-transfer agent (CTA) capable of reducing the required amount of metal complex while still maintaining full control over the living polymerization process. This new method introduces a degenerative transfer process to ROMP. We demonstrate that substituted cyclohexene rings are good CTAs, and thereby preserve the ‘living’ character of the polymerization using catalytic quantities of the metal complex. The resulting polymers show characteristics of a living polymerization, namely narrow molecular-weight distribution, controlled molecular weights and block copolymer formation. This new technique provides access to well-defined polymers for industrial, biomedical and academic use at a fraction of the current costs and significantly reduced levels of residual ruthenium catalyst.

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Figure 1: Illustration of catalytic living ROMP.
Figure 2: Possible reactions of CTA1 with the G3 benzylidene complex.
Figure 3: The mechanism of the process of degenerative chain-transfer metathesis.
Figure 4: Plot of the molecular weight obtained versus the monomer/CTA ratio.

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  • 11 April 2018

    We the authors are retracting this Article because of our failure to reproduce the molecular weight dispersities (PDI) shown in Fig. 4 using the chain-transfer agent described in the paper (CTA1). While the degenerate chain-transfer mechanism described in Fig. 3 is correct, the best molecular weight dispersities that could be reproduced with the chain-transfer agent shown in the Article are much larger (PDI > 2.0) than reported. We have since studied the kinetics of CTA1 in comparison with several other chain-transfer agents we are currently investigating and we now understand that the reactivity of CTA1 towards propagating ruthenium alkylidene complexes is very low. Very long monomer addition times would therefore have been necessary to gain control over the molecular weight distribution. Such long addition times would exceed the lifetime of the Grubbs catalyst in solution. Faster addition of the monomer has since repeatedly been shown to broaden the molecular weight dispersity. Additionally, the best chain-transfer agents we are currently investigating are orders of magnitude more reactive than CTA1 but give broader molecular weight dispersities than reported in Fig. 4. Molecular weight and dispersity control as shown in Fig. 4 is therefore an inappropriate claim for CTA1. The authors deeply regret these errors and apologize to the community.

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Acknowledgements

The authors thank the Swiss National Science Foundation for funding.

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  1. Department of Chemistry, University of Fribourg, Chemin du Musée 9, Fribourg, CH-1700, Switzerland

    Amit A. Nagarkar & Andreas F. M. Kilbinger

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  1. Amit A. Nagarkar
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Contributions

A.A.N. and A.F.M.K. designed the experiments. A.A.N. performed the experiments. A.A.N. and A.F.M.K. wrote the main manuscript. Both authors reviewed the manuscript.

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Correspondence to Andreas F. M. Kilbinger.

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Nagarkar, A., Kilbinger, A. Catalytic living ring-opening metathesis polymerization. Nature Chem 7, 718–723 (2015). https://doi.org/10.1038/nchem.2320

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