Mechanism of carbon-halogen bond reductive cleavage in activated alkyl halide initiators relevant to living radical polymerization: Theoretical and experimental study

Abdirisak A. Isse, Armando Gennaro*, Ching Yeh Lin, Jennifer L. Hodgson, Michelle L. Coote, Tamaz Guliashvili

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    135 Citations (Scopus)

    Abstract

    The mechanism of reductive cleavage of model alkyl halides (methyl 2-bromoisobutyrate, methyl 2-bromopropionate, and 1-bromo-1-chloroethane), used as initiators in living radical polymerization (LRP), has been investigated in acetonitrile using both experimental and computational methods. Both theoretical and experimental investigations have revealed that dissociative electron transfer to these alkyl halides proceeds exclusively via a concerted rather than stepwise manner. The reductive cleavage of all three alkyl halides requires a substantial activation barrier stemming mainly from the breaking C-X bond. The activation step during single electron transfer LRP (SET-LRP) was originally proposed to proceed via formation and decomposition of RX•- through an outer sphere electron transfer (OSET) process (Guliashvili, T.; Percec, V.J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 1607). These radical anion intermediates were proposed to decompose via heterolytic rather than homolytic C-X bond dissociation. Here it is presented that injection of one electron into RX produces only a weakly associated charge-induced donor-acceptor type radical anion complex without any significant covalent α type bond character between carbon-centered radical and associated anion leaving group. Therefore, neither homolytic nor heterolytic bond dissociation applies to the reductive cleavage of C-X in these alkyl halides inasmuch as a true radical anion does not form in the process. In addition, the whole mechanism of SET-LRP has to be revisited since it is based on presumed OSET involving intermediate RX•-, which is shown here to be nonexistent.

    Original languageEnglish
    Pages (from-to)6254-6264
    Number of pages11
    JournalJournal of the American Chemical Society
    Volume133
    Issue number16
    DOIs
    Publication statusPublished - 27 Apr 2011

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