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

Research output: Contribution to journalArticlepeer-review


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
Issue number16
StatePublished - Apr 24 2019

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization'. Together they form a unique fingerprint.

Cite this