A Hydrometalation Initiation Mechanism via a Discrete Cobalt-Hydride for a Rapid and Controlled Radical Polymerization

Sajjad Dadashi-Silab, Erin E. Stache

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Cobalt-mediated radical polymerization (CMRP) is a versatile technique for controlling the polymerization of vinyl monomers via reversible termination using CoII complexes as persistent radical deactivators. Here, we report a facile approach for the in situ generation of Co-H as a discrete initiator and mediator for CMRP of acrylate and acrylamide monomers, overcoming the limitations of existing initiation strategies. In situ oxidation of a CoII complex followed by transmetalation with silane generates a Co-H species, which initiates polymerization via hydrometalation of the monomer. This method precludes an induction period with excellent control over targeted molecular weight and dispersity. Strikingly, our approach allows complete polymerization when the induction period ends for conventional CMRP. A broad scope of monomers is amenable to this protocol, including acrylates and acrylamides. Tunable catalyst electronics afford tailored dispersity while maintaining agreement in molecular weight in stark contrast to conventional methods. Elimination of this induction period imbues polymerization behavior entirely to the catalyst electronic effects on reversible deactivation/activation rates.

Original languageEnglish (US)
Pages (from-to)13311-13318
Number of pages8
JournalJournal of the American Chemical Society
Volume144
Issue number29
DOIs
StatePublished - Jul 27 2022
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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