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

3 Citations (Scopus)

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

Fingerprint

Polymerization
Living polymerization
Polyolefins
Dimers
Palladium
Olefins
Monomers
Molecular weight
Alkenes
Molecular Weight
carbene
diazoacetic ester
PL 732

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., ... 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
Zhukhovitskiy, Aleksandr V. ; Kobylianskii, Ilia J. ; Thomas, Andy A. ; Evans, Austin M. ; Delaney, Connor P. ; Flanders, Nathan C. ; Denmark, Scott E. ; DIchtel, William R. ; Toste, F. Dean. / A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 16. pp. 6473-6478.
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Zhukhovitskiy, AV, Kobylianskii, IJ, Thomas, AA, Evans, AM, Delaney, CP, Flanders, NC, Denmark, SE, DIchtel, WR & Toste, FD 2019, 'A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization', Journal of the American Chemical Society, vol. 141, no. 16, pp. 6473-6478. https://doi.org/10.1021/jacs.9b01532

A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization. / Zhukhovitskiy, Aleksandr V.; Kobylianskii, Ilia J.; Thomas, Andy A.; Evans, Austin M.; Delaney, Connor P.; Flanders, Nathan C.; Denmark, Scott E.; DIchtel, William R.; Toste, F. Dean.

In: Journal of the American Chemical Society, Vol. 141, No. 16, 24.04.2019, p. 6473-6478.

Research output: Contribution to journalArticle

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AU - Zhukhovitskiy, Aleksandr V.

AU - Kobylianskii, Ilia J.

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AU - Delaney, Connor P.

AU - Flanders, Nathan C.

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AB - 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.

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Zhukhovitskiy AV, Kobylianskii IJ, Thomas AA, Evans AM, Delaney CP, Flanders NC et al. A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization. Journal of the American Chemical Society. 2019 Apr 24;141(16):6473-6478. https://doi.org/10.1021/jacs.9b01532