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Redox-switchable olefin cross metathesis (CM) reactions and acyclic diene metathesis (ADMET) polymerizations

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Abstract

We show that redox-switchable catalysis may be used to control acyclic diene metathesis (ADMET) polymerizations and related reactions. A Ru(II) complex was found to display catalytic activities that were dependent on the oxidation state of a quinone-containing ligand. While the neutral form of the complex was found to catalyze ADMET polymerizations at rates that were commensurate with a commercially-available catalyst, significantly lower activities were observed when the complex was reduced. Using the rate differential, a series of ADMET polymerizations were modulated by alternately reducing and oxidizing the catalyst over time. A similar approach was also used to regulate the molecular weights of the polymers produced. Cross metathesis reactions and computational studies were performed in parallel to gain a deeper understanding of the underlying redox-switchable chemistry.

Graphical abstract: Redox-switchable olefin cross metathesis (CM) reactions and acyclic diene metathesis (ADMET) polymerizations

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Publication details

The article was received on 15 Jun 2019, accepted on 31 Jul 2019 and first published on 12 Aug 2019


Article type: Research Article
DOI: 10.1039/C9QM00391F
Mater. Chem. Front., 2019, Advance Article

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    Redox-switchable olefin cross metathesis (CM) reactions and acyclic diene metathesis (ADMET) polymerizations

    Y. Ryu, H. Shao, G. Ahumada, P. Liu and C. W. Bielawski, Mater. Chem. Front., 2019, Advance Article , DOI: 10.1039/C9QM00391F

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