Highly active ruthenium metathesis catalysts enabling ring-opening metathesis polymerization of cyclopentadiene at low temperatures

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Development of versatile ruthenium olefin-metathesis catalysts with high activity, stability, and selectivity is a continuous challenge. Here we report highly controllable ruthenium catalysts using readily accessible and versatile N-vinylsulfonamides as carbene precursors. Catalyst initiation rates were controlled in a straightforward manner, from latent to fast initiating, through the facile modulation of the N-vinylsulfonamide ligands. Trifluoromethanesulfonamide-based catalysts initiated ultrarapidly even at temperatures as low as -60 degrees C and continuously propagated rapidly, enabling the enthalpically and entropically less-favored ring-opening metathesis polymerizations of low-strained functionalized cyclopentene derivatives, some of which are not accessible with previous olefin-metathesis catalysts. To our surprise, the developed catalysts facilitated the polymerization of cyclopentadiene (CPD), a feedstock that is easily and commonly obtainable through the steam cracking of naphtha, which has, to the best of our knowledge, not been previously achieved due to its low ring strain and facile dimerization even at low temperatures (below 0 degrees C).
Publisher
NATURE PUBLISHING GROUP
Issue Date
2019-08
Language
English
Article Type
Article
Citation

NATURE COMMUNICATIONS, v.10

ISSN
2041-1723
DOI
10.1038/s41467-019-11806-5
URI
http://hdl.handle.net/10203/267531
Appears in Collection
CH-Journal Papers(저널논문)
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