A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization

Aleksandr V. Zhukhovitskiy, Ilia J. Kobylianskii, Andy A. Thomas, Austin M. Evans, Connor P. Delaney, Nathan C. Flanders, Scott E. Denmark, William R. DIchtel, F. Dean Toste*

*Corresponding author for this work

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (?-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2-1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

Original languageEnglish (US)
Pages (from-to)6473-6478
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number16
DOIs
StatePublished - Apr 24 2019

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Zhukhovitskiy, A. V., Kobylianskii, I. J., Thomas, A. A., Evans, A. M., Delaney, C. P., Flanders, N. C., Denmark, S. E., DIchtel, W. R., & Toste, F. D. (2019). A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization. Journal of the American Chemical Society, 141(16), 6473-6478. https://doi.org/10.1021/jacs.9b01532