Synergetic Effect of Monomer Functional Group Coordination in Catalytic Insertion Polymerization

Journal of the American Chemical Society
Hannes LeichtStefan Mecking

Abstract

PhS- and PhNH-functionalized dienes are copolymerized efficiently with butadiene to stereoregular copolymers by [(mesitylene)Ni(allyl)][BArF4] (Ni-1). Overall polymerization rates and comonomer incorporations depend strongly on the linker length between the diene moiety and functional group, in, e.g., PhS-(CH2)xC(═CH2)-CH═CH2 (PhS-x-BD, x = 3-7), in particular for certain linker lengths high comonomer reactivity ratios stand out. This effect is related to a favorable binding of the comonomer to the active site comprising coordination of its functional group, which significantly enhances comonomer incorporation in the growing polymer chain.

References

Mar 21, 2007·Journal of the American Chemical Society·Abby R O'ConnorMaurice Brookhart
Oct 8, 2009·Chemical Reviews·Akifumi NakamuraKyoko Nozaki
Mar 9, 2010·Journal of the American Chemical Society·Damien GuironnetStefan Mecking
Jan 5, 2012·Journal of the American Chemical Society·Tobias FriedbergerStefan Mecking
Jan 10, 2012·Journal of the American Chemical Society·Madalyn R RadlauerTheodor Agapie

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Citations

Sep 20, 2018·Organic & Biomolecular Chemistry·Jesús Flores-FerrándizVittorio Caprio
Jan 28, 2020·Angewandte Chemie·Jiazhen ChenTobin J Marks
Jul 13, 2018·Chemical Science·Yangbin LiuClément Mazet
Aug 12, 2021·Journal of the American Chemical Society·Daniele FioritoClément Mazet
Aug 3, 2019·Journal of the American Chemical Society·Jill B WilliamsonFrank A Leibfarth

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