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Bellone DE, Bours J, Menke EH, et al. Highly selective molybdenum ONO pincer complex initiates the living ring-opening metathesis polymerization of strained alkynes with exceptionally low polydispersity indices. J Am Chem Soc. 2015;137(2):850-6doi: 10.1021/ja510919v.
Bellone, D. E., Bours, J., Menke, E. H., & Fischer, F. R. (2015). Highly selective molybdenum ONO pincer complex initiates the living ring-opening metathesis polymerization of strained alkynes with exceptionally low polydispersity indices. Journal of the American Chemical Society, 137(2), 850-6. https://doi.org/10.1021/ja510919v
Bellone, Donatela E, et al. "Highly selective molybdenum ONO pincer complex initiates the living ring-opening metathesis polymerization of strained alkynes with exceptionally low polydispersity indices." Journal of the American Chemical Society vol. 137,2 (2015): 850-6. doi: https://doi.org/10.1021/ja510919v
Bellone DE, Bours J, Menke EH, Fischer FR. Highly selective molybdenum ONO pincer complex initiates the living ring-opening metathesis polymerization of strained alkynes with exceptionally low polydispersity indices. J Am Chem Soc. 2015 Jan 21;137(2):850-6. doi: 10.1021/ja510919v. Epub 2015 Jan 06. PMID: 25535767; PMCID: PMC4308759.
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J Am Chem Soc. 2015 Jan 21;137(2):850-6. doi: 10.1021/ja510919v. Epub 2015 Jan 06.

Highly selective molybdenum ONO pincer complex initiates the living ring-opening metathesis polymerization of strained alkynes with exceptionally low polydispersity indices.

Journal of the American Chemical Society

Donatela E Bellone, Justin Bours, Elisabeth H Menke, Felix R Fischer

Affiliations

  1. Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States.

PMID: 25535767 PMCID: PMC4308759 DOI: 10.1021/ja510919v

Abstract

The pseudo-octahedral molybdenum benzylidyne complex [TolC≡Mo(ONO)(OR)]·KOR (R = CCH3(CF3)2) 1, featuring a stabilizing ONO pincer ligand, initiates the controlled living polymerization of strained dibenzocyclooctynes at T > 60 °C to give high molecular weight polymers with exceptionally low polydispersities (PDI ∼ 1.02). Kinetic analyses reveal that the growing polymer chain attached to the propagating catalyst efficiently limits the rate of propagation with respect to the rate of initiation (kp/ki ∼ 10(-3)). The reversible coordination of KOCCH3(CF3)2 to the propagating catalyst prevents undesired chain-termination and -transfer processes. The ring-opening alkyne metathesis polymerization with 1 has all the characteristics of a living polymerization and enables, for the first time, the controlled synthesis of amphiphilic block copolymers via ROAMP.

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